TW201900859A - Liquid detergent composition for hard surfaces - Google Patents

Abstract

The present invention is a liquid detergent composition for hard surfaces, which contains: (a) a copolymer that comprises a specific constituent unit (a1) having a betaine group and a specific constituent unit (a2) having a cation group, with the molar ratio of the constituent unit (a1) to the constituent unit (a2), namely (constituent unit (a1))/(constituent unit (a2)) being from 30/70 to 99.9/0.1 (inclusive); (b) a cationic surfactant; and (c) one or more surfactants selected from among amphoteric surfactants, nonionic surfactants and anionic surfactants.

Description

Liquid detergent composition for hard surfaces

The present invention relates to a liquid detergent composition for a hard surface and a method for preventing dirt from adhering to a hard surface.

There are various hard surfaces on the living environment equipment, such as tiles, plastics, metals, etc., which are exposed to the environment in which various dirt is adhered in the living scene. Among them, the hard surface used as a bathroom, a bathroom, a kitchen, and the like is also a surface that is in daily contact with a person, and therefore has a property of easily remaining and accumulating a large amount of dirt, which is difficult to wash and remove.

For example, Japanese Laid-Open Patent Publication No. 2010-100861 discloses a hard surface cleaning or rinsing composition comprising at least one surfactant and at least one polybetaine (B). A composition for washing or rinsing a hard surface in an aqueous medium or an aqueous alcohol medium, the polybetaine (B) having a constant total anion charge and a constant total cationic charge in a pH range of from 1 to 14 (each betaine) The unit has a constant cationic charge with the same amount of invariant anionic charge) and exhibits an absolute weight average molecular weight (Mw) of 5,000 to 3,000,000 g/mole. Further, in the specification of U.S. Patent Application Publication No. 2009/0197791, a copolymer comprising a unit A containing a beet base and a cationic unit B is disclosed.

It is not sufficient to satisfy the foaming ability, the sterilization performance, and the antifouling property in the specification of Japanese Patent Laid-Open Publication No. 2010-100861, and U.S. Patent Application Publication No. 2009/0197791. In particular, the present inventors have found that when a polymer having a beet base described in Japanese Patent Laid-Open Publication No. 2010-100861 is used in combination with a cationic surfactant, it is further used to improve foaming ability. Other surfactants, such as nonionic surfactants, amphoteric surfactants, or anionic surfactants, have reduced antifouling properties on hard surfaces.

Further, the specification of the Japanese Patent Laid-Open Publication No. 2010-100861, and the specification of the US Patent Application Publication No. 2009/0197791 is difficult to satisfy the scale removal detergency (hereinafter also referred to as detergency), the sterilization performance, and the antifouling property. Full of words. In particular, the inventors of the present invention have found that when a polymer having a beet base described in Japanese Patent Laid-Open Publication No. 2010-100861 is used in combination with a cationic surfactant, it is further used to improve the detergency. The chelating agent reduces the antifouling properties of the hard surface.

The present invention relates to a liquid detergent composition for a hard surface which is excellent in foaming performance, excellent in foaming ability, and excellent in adhesion prevention of dirt to a hard surface or the like, that is, excellent in antifouling performance.

The present invention relates to a liquid detergent composition for a hard surface which is capable of maintaining sterilization performance, is excellent in detergency, and is excellent in adhesion of dirt to a hard surface, that is, excellent in antifouling performance.

The present inventors have found that by using a polymer having a specific beet base, a specific cationic group, a cationic surfactant, and a nonionic surfactant, an amphoteric surfactant or an anionic surfactant It is possible to obtain an effect of excellent antifouling performance, foaming ability (hereinafter also referred to as foaming property), and sterilization performance.

The present invention provides a hard surface liquid detergent composition comprising: (a) a structural unit (a1) represented by the following formula (1); and a structural unit represented by the following formula (2) (a2) And the molar ratio of the structural unit (a1) to the structural unit (a2), that is, the structural unit (a1)/structural unit (a2) is a copolymer of 30/70 or more and 99.9/0.1 or less, and (b) cationic interface activity And (c) one or more surfactants selected from the group consisting of an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant [hereinafter referred to as component (c)].

[Chemical 1]

Wherein R ¹ to R ^{3 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; and R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, or -Y ¹ -OPO ₃ ^- - Y ² -, Y ¹ and Y ^{2 are the} same or different and are an alkylene group having 1 or more and 4 or less carbon atoms, and R ⁵ and R ^{6 are the} same or different, and are a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ¹ is O. Or NR ⁷ , R ⁷ is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ² represents a hydrogen atom, a hydrocarbon group having 1 or more and 4 or less carbon atoms, R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- ; When R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, X ² is R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- , and R ¹⁷ is an alkylene group having 1 or more and 4 or less carbon atoms, and is R ^{4 .} When -Y ¹ -OPO ₃ ^- -Y ² -, X ² is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms]

[Chemical 2]

Wherein R ⁸ to R ^{10 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; X ³ is O; R ¹¹ is an alkylene group having 1 or more and 4 or less carbon atoms, and X ⁴ is N. ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ , and R ¹² to R ^{16 are the} same or different and each represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ⁵ represents an anion]

Further, the inventors of the present invention have found that antifouling properties, detergency, and removal can be obtained by using a polymer having a specific beet base and a specific cationic group, a cationic surfactant, and a chelating agent. Excellent bacterial performance.

The present invention relates to a liquid detergent composition for a hard surface, comprising: (a) a structural unit (a1) represented by the following formula (1), and a structural unit represented by the following formula (2) ( A2) and the molar ratio of the structural unit (a1) to the structural unit (a2), that is, the structural unit (a1)/structural unit (a2) is a copolymer of 30/70 or more and 99.9/0.1 or less [hereinafter referred to as (a) Component], (b) a cationic surfactant (hereinafter referred to as component (b)), and (d) a chelating agent (hereinafter referred to as component (d)).

[Chemical 3]

Wherein R ¹ to R ^{3 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; and R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, or -Y ¹ -OPO ₃ ^- - Y ² -, Y ¹ and Y ^{2 are the} same or different and are an alkylene group having 1 or more and 4 or less carbon atoms, and R ⁵ and R ^{6 are the} same or different, and are a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ¹ is O. Or NR ⁷ , R ⁷ is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ² represents a hydrogen atom, a hydrocarbon group having 1 or more and 4 or less carbon atoms, R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- ; When R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, X ² is R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- , and R ¹⁷ is an alkylene group having 1 or more and 4 or less carbon atoms, and is R ^{4 .} When -Y ¹ -OPO ₃ ^- -Y ² -, X ² is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms]

[Chemical 4]

Wherein R ⁸ to R ^{10 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; X ³ is O; R ¹¹ is an alkylene group having 1 or more and 4 or less carbon atoms, and X ⁴ is N. ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ , and R ¹² to R ^{16 are the} same or different and each represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ⁵ represents an anion]

Hereinafter, in the case of the hard surface liquid detergent composition of the present invention, the above two types of hard surface liquid detergent compositions are included.

Further, the present invention relates to a method for preventing adhesion of dirt on a hard surface by treating the hard surface with the above-described liquid detergent composition for a hard surface of the present invention.

According to the present invention, there is provided a liquid detergent composition for a hard surface which is excellent in foaming performance, excellent in foaming ability, and excellent in adhesion of dirt to a hard surface, that is, excellent in antifouling performance.

Moreover, according to the present invention, there is provided a liquid detergent composition for a hard surface which is capable of maintaining sterilization performance, is excellent in detergency, and is excellent in antifouling performance, that is, adhesion of dirt to a hard surface.

[Solid surface liquid detergent composition] The hard surface liquid detergent composition of the present invention is a liquid surface containing a hard surface containing (a) component, (b) component, and (c) component in one aspect. Detergent composition. <Component (a)> The component (a) is a copolymer comprising the structural unit (a1) represented by the above formula (1) and the structural unit (a2) represented by the above formula (2). The structural unit (a1) represented by the above formula (1) may be a structural unit derived from an unsaturated monomer having a beet base. Further, the structural unit (a2) represented by the above formula (2) may be a structural unit derived from an unsaturated monomer having a cationic group.

[(a) Weight average molecular weight of the component] The weight average molecular weight of the component (a) is preferably 500 or more, more preferably 5,000 or more, and still more preferably 1 in terms of improving the antifouling property of the component (a). More preferably, it is 30,000 or more, and more preferably 30,000 or more, and from the same viewpoint, it is preferably 200,000 or less, more preferably 150,000 or less, and still more preferably 100,000 or less. The weight average molecular weight can be measured by the method described in the examples.

[Mohr ratio of structural unit (a1) and structural unit (a2)] From the viewpoint of antifouling performance, the molar ratio of the structural unit (a1) of the component (a) to the structural unit (a2) is a structural unit ( The a1)/structural unit (a2) is calculated to be 30/70 or more and 99.9/0.1 or less. From the same viewpoint, the moieties of the structural unit (a1)/structural unit (a2) are preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, and still more preferably 75/25 or more, and more preferably 90/10 or more, and from the viewpoint of improving the antifouling performance of the component (a), it is preferably 98/2 or less, more preferably 96/4 or less.

[Structural unit (a1)] (content of structural unit (a1)) The content of the structural unit (a1) in the component (a) is preferably 30 mol from the viewpoint of improving the antifouling property of the component (a). More preferably, it is 50 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, and still more preferably 90 mol% or more, and from the same viewpoint, It is preferably 99% by mole or less, more preferably 98% by mole or less, still more preferably 95% by mole or less. Further, from the viewpoint of improving the antifouling performance of the component (a), the content of the structural unit (a1) in the component (a) is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and from the same viewpoint, it is preferably 99% by mass or less, more preferably 98% by mass or less, and further preferably It is 95% by mass or less.

(Configuration of Structural Unit (a1)) The structural unit (a1) of the component (a) is a structural unit represented by the following formula (1).

[Chemical 5]

Wherein R ¹ to R ^{3 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; and R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, or -Y ¹ -OPO ₃ ^- - Y ² - Y ¹ and Y ^{2 are the} same or different and are an alkylene group having 1 or more and 4 or less carbon atoms, and R ⁵ and R ^{6 are the} same or different, and are a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ¹ is O or NR ⁷ and R ⁷ are a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ² represents a hydrogen atom, a hydrocarbon group having 1 or more and 4 or less carbon atoms, R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- ; When R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, X ² is R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- , and R ¹⁷ is an alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴ is -Y ¹ -OPO ₃ ^- -Y ² -, X ² is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms]

In the formula (1), from the viewpoint of the availability of the unsaturated monomer, the viewpoint of the polymerizability of the monomer, and the improvement of the antifouling property of the component (a), R ¹ and R ² are preferably each. A hydrogen atom. In the formula (1), R ^{3 is} preferably a hydrogen atom or a viewpoint from the viewpoint of the availability of the unsaturated monomer, the viewpoint of the polymerization property of the monomer, and the improvement of the antifouling property of the component (a). More preferably, it is a methyl group. In the formula (1), X ^{1 is} preferably O from the viewpoint of the availability of the unsaturated monomer, the viewpoint of the polymerizability of the monomer, and the improvement of the antifouling property of the component (a). From the same viewpoint, the alkylene group having 1 or more and 4 or less carbon atoms of R ⁴ is preferably a C 2 or 3 alkylene group, more preferably a C 2 alkylene group. In the formula (1), R ^{4 is} preferably an alkylene group having 1 or more and 4 or less carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms, from the viewpoint of improving the antifouling property. In the formula (1), Y ¹ and Y ² are each preferably a C 2 or 3 alkylene group, more preferably a C 2 alkylene group. In the formula (1), R ⁵ and R ⁶ are preferably each from the viewpoint of the availability of the unsaturated monomer, the viewpoint of the polymerizability of the monomer, and the improvement of the antifouling property of the component (a). It is a methyl group or an ethyl group, more preferably a methyl group. In the formula (1), X ² is a hydrogen atom, a hydrocarbon group having 1 or more and 4 or less carbon atoms, R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- , and R ⁴ is a hydrocarbon having 1 or more and 4 or less carbon atoms. In the case of a group, X ² is R ¹⁷ SO ₃ ^- or COO ^- , and when R ⁴ is -Y ¹ -OPO ₃ ^- -Y ² -, X ² is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. When R ⁴ is -Y ¹ -OPO ₃ ^- -Y ² -, X ^{2 is} preferably a hydrocarbon group having 1 or more and 4 or less carbon atoms, and more preferably a methyl group, from the viewpoint of improving the antifouling performance. When R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, X ^{2 is} preferably R ¹⁷ SO ₃ ^{- from the} same viewpoint. Further, R ^{17 is} preferably an alkylene group having 1 or more and 3 or less carbon atoms, more preferably an alkylene group having 2 or more and 3 or less carbon atoms.

[Structural unit (a2)] (content of the structural unit (a2)) The content of the structural unit (a2) in the component (a) is preferably 1 mol% or more, more preferably from the viewpoint of improving the antifouling performance. It is 2 mol% or more, more preferably 5 mol% or more, and from the same viewpoint, it is preferably 70 mol% or less, more preferably 50 mol% or less, and still more preferably 30 mol%. % or less is further preferably 20 mol% or less, and further preferably 10 mol% or less. In addition, the content of the structural unit (a2) in the component (a) is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass or more, from the viewpoint of improving the antifouling performance. In view of improving the antifouling performance of the component (a), it is preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, and further preferably 20% by mass or less. Further, it is preferably 10% by mass or less.

(Configuration of Structural Unit (a2)) The structural unit (a2) of the component (a) is a structural unit represented by the following formula (2).

[Chemical 6]

Wherein R ⁸ to R ^{10 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, X ³ is O or NH, and R ¹¹ is an alkylene group having 1 or more and 4 or less carbon atoms, and X ⁴ N ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ , and R ¹² to R ^{16 are the} same or different and each represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ⁵ represents an anion]

In the formula (2), from the viewpoint of the availability of the unsaturated monomer, the viewpoint of the polymerizability of the monomer, and the improvement of the antifouling property of the component (a), R ⁸ and R ⁹ are preferably each. A hydrogen atom. In the formula (2), R ^{10 is} preferably a hydrogen atom or a methyl group from the viewpoint of the polymerizability of the monomer and the antifouling property of the component (a), and more preferably a methyl group. In the formula (2), X ^{3 is} preferably O from the viewpoint of the polymerizability of the monomer and the improvement of the antifouling property of the component (a). In the formula (2), R ^{11 is} preferably a C 2 or 3 alkylene group, more preferably carbon, from the viewpoint of the polymerizability of the monomer and the antifouling property of the component (a). Number 2 of the alkyl group. In the formula (2), X ⁴ is N ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R from the viewpoint of improving the antifouling property of the component (a) and the easiness of the quaternization reaction. ^{16 is} preferably N ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ , and from the same viewpoint, R ¹² , R ¹³ and R ¹⁴ are each preferably a methyl group or an ethyl group. In the formula (2), R ¹⁵ and R ^{16 are} preferably a methyl group or an ethyl group, and more preferably a viewpoint of improving the antifouling property of the component (a) and the easiness of the quaternization reaction. methyl. In the formula (2), X ⁵ is an anion, preferably a halogen ion or C ₂ H ₅ SO ₄ ^- , more preferably C ₂ H ₅ SO ₄ ^- .

[Structural unit other than the structural unit (a1) and the structural unit (a2)] The component (a) may contain a structural unit other than the structural unit (a1) and the structural unit (a2) within a range that does not impair the effects of the present invention. The structural unit other than the structural unit (a1) and the structural unit (a2) is preferably a structural unit derived from an unsaturated monomer other than the unsaturated monomer having a sulfobeine base, more preferably hydrophobic from styrene or the like. A structural unit of a monounsaturated monomer.

The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 10 mol% or less, more preferably 5 mol% or less, from the viewpoint of antifouling property. It is more preferably 1 mol% or less, further preferably 0.5 mol% or less, and still more preferably 0.1 mol% or less. The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) may be 0 mol%.

From the viewpoint of the antifouling property, the content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 10% by mass or less, more preferably 5% by mass or less, and further It is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.1% by mass or less. The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) may be 0% by mass.

In view of the antifouling property, the total content of the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably It is 99 mol% or more, more preferably 99.5 mol% or more, and still more preferably 99.9 mol% or more. The total content of the structural unit (a1) and the structural unit (a2) in the component (a) may be 100 mol%. In view of the antifouling property, the total content of the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 99%. The molar percentage is more than or equal to 90% by mass, more preferably 99.9% by mass or more. The total content of the structural unit (a1) and the structural unit (a2) in the component (a) may be 100% by mass.

[Method for Producing Component (a)] As the method for producing the component (a), any method may be employed, and specific examples thereof include the methods (i) and (ii) below. The method of (ii) is preferred from the viewpoint of availability of raw materials and ease of manufacture. (i) a method obtained by copolymerizing an unsaturated monomer having a beet base and a cationic group, (ii) a copolymerization of an unsaturated monomer having an amino group and a cationic group, followed by a betaining agent Method of obtaining four levels

<(b) component> The component (b) is a cationic surfactant. As the cationic surfactant, a mono- or di-long-chain alkyl type quaternary ammonium salt is preferred. The component (b) is preferably a cationic surfactant selected from the group consisting of a compound represented by the following formula (b1) and a compound represented by the formula (b2).

[Chemistry 7]

In the formula, at least one selected from the group consisting of R ^1b and R ^2b represents an alkyl group having 8 or more and 18 or less carbon atoms, an alkenyl group having 8 or more and 18 or less carbon atoms, or a hydroxyalkyl group having 8 or more and 18 or less carbon atoms. The remainder represents an alkyl group having 1 or more and 3 or less carbon atoms, a hydroxyalkyl group having 1 or more and 3 or less carbon atoms, or a polyoxyalkylene group having an average addition molar number of 10 or less, and R ^3b and R ^{4b are the} same or different. Each represents an alkyl group having 1 or more and 3 or less carbon atoms, a hydroxyalkyl group having 1 or more and 3 or less carbon atoms, or a polyoxyalkylene group having an average addition molar number of 10 or less, and Y ^- represents a halogen atom or a carbon number of 1 Above and below 5 or less anion residues of sulfonate or sulfate]

[化8]

In the formula, R ^5b represents an alkyl group having 8 or more and 18 or less carbon atoms, an alkenyl group having 8 or more and 18 or less carbon atoms, or a hydroxyalkyl group having 8 or more and 18 or less carbon atoms, and R ^6b and R ^{7b are the} same or different. Each represents an alkyl group having 1 or more and 3 or less carbon atoms, a hydroxyalkyl group having 1 or more and 3 or less carbon atoms, or a polyoxyalkylene group having an average addition molar number of 10 or less, and R ^8b represents a carbon number of 1 or more and 3 or less. An alkyl group; Z ^- represents a halogen atom, or an anion residue of a sulfonate or sulfate having a carbon number of 1 or more and 5 or less]

In the case of a single long-chain alkyl type quaternary ammonium salt, in the formula (b1), R ^1b is preferably an alkyl group, an alkenyl group or a hydroxyalkyl group having a carbon number of 8 or more and 16 or less, R ^2b , ^R3b and ^{R4b are the} same or different and each is an alkyl group having 1 or more and 3 or less carbon atoms, a hydroxyalkyl group or a polyoxyalkylene group having an average addition of 10 or less moles. In the case of a di-long-chain alkyl type quaternary ammonium salt, in the formula (b1), R ^1b and R ^2b are preferably the same or different, and each is an alkyl group having 8 or more and 16 or less carbon atoms. Alkenyl or hydroxyalkyl, R ^3b and R ^{4b are the} same or different and each is an alkyl group having 1 or more and 3 or less carbon atoms, a hydroxyalkyl group or a polyoxyethylene group having an average addition molar number of 10 or less.

In the formula (b2), R ^{5b is} preferably a linear alkyl group having 12 or more and 16 or less carbon atoms, R ^6b and R ^7b are each preferably a methyl group, R ^{8b is} preferably a methylene group, and Z ^- is A halogen ion is further preferably a chloride ion (Cl ^- ).

The component (b) is preferably a cationic surfactant selected from the compounds represented by the above formula (b2).

<Component (c)> The component (c) is at least one selected from the group consisting of an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant. From the viewpoint of the stability of the formulation, the component (c) is preferably one or more surfactants selected from the group consisting of an amphoteric surfactant and a nonionic surfactant.

[Amphoteric surfactant] As an amphoteric surfactant, it is preferred to contain one or more kinds of amphoteric interfaces selected from the group consisting of amine oxides, sulfobetaines, and carboxybetaines from the viewpoint of blending stability and foaming properties. The active agent is more preferably one or more kinds of an amphoteric surfactants selected from the group consisting of sulfobetaine and carboxybetaine, and more preferably carboxybetaine. These may also be used in two or more types.

In the amphoteric surfactant, the content of one or more kinds of the amphoteric surfactants selected from the group consisting of amine oxides, sulfobetaines, and carboxybetaines is preferably 50% by mass in terms of blending stability and foaming properties. The above is more preferably 70% by mass or more, further preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and more preferably 100% by mass or less. Further, in the amphoteric surfactant, the content of one or more kinds of the amphoteric surfactants selected from the group consisting of sulfobetaine and carboxybetaine is preferably 50% by mass or more from the viewpoint of blending stability and foaming property. More preferably, it is 70% by mass or more, further preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and more preferably 100% by mass. Below mass%.

The sulfobetaine may, for example, be an alkyl group having a carbon number of preferably 10 or more, and preferably 18 or less, more preferably 14 or less, from the viewpoint of blending stability and foaming property. -N,N-dimethyl-N-sulfopropyl ammonium sulfobetaine; the carbon number of the alkyl group is preferably 10 or more, and preferably 18 or less from the viewpoint of blending stability and foaming property More preferably, it is an N-alkyl-N,N-dimethyl-N-(2-hydroxysulfonyl)ammonium sulfobetaine of 14 or less; from the viewpoint of blending stability and foaming properties, an alkane The carbon number of the fluorenyl group is preferably 10 or more, and preferably 18 or less, more preferably 14 or less N-alkylmercaptopropyl propyl-N,N-dimethyl-N-sulfopropyl ammonium sulfo group Betaine; the alkyl group has a carbon number of preferably 10 or more, and preferably 18 or less, more preferably 14 or less N-alkyldecylaminopropyl, from the viewpoint of blending stability and foaming property. -N,N-Dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine.

The carboxybetaine may, for example, be an alkyl group having a carbon number of preferably 10 or more, and preferably 18 or less, more preferably 14 or less, from the viewpoint of blending stability and foaming property. N,N-dimethyl-N-carboxymethylammonium betaine; or a compound represented by the following formula (I); from the viewpoint of formulation stability and foaming property, the following formula is preferred (I) The compound represented.

[Chemistry 9]

In the formula, R ^1c represents an alkyl group or an alkenyl group having 7 or more and 21 or less carbon atoms, R ^2c represents a propyl group, and R ^3c and R ^4c each independently represent an alkyl group having 1 or more and 3 or less carbon atoms]

In the general formula (I), R ^1c is preferably 9 or more, more preferably 11 or more, and is preferably 15 or less, more preferably 13 or less, from the viewpoint of blending stability and foaming property. Or an alkenyl group, preferably an anthracenyl group, a fluorenyl group, an undecyl group, a dodecyl group or a tridecyl group. In the general formula (I), R ^3c and R ^{4c are} preferably a methyl group from the viewpoint of blending stability and foaming property. Examples of the compound represented by the formula (I) include amygdalin propylamine betaine, apricot aglycone propyl betaine, avocado oil guanamine propyl betaine, and babassu amiodalide. Betaine, behenyl propyl betaine, rapeseed oil guanamine propyl betaine, thiol/prolinyl propyl betaine, cocoamidopropyl betaine, coconut oil/oil amide Betaine, isostearyl propylamine betaine, lauryl propyl carboxybetaine, milk amidoxime betaine, guanidine propylamine betaine, myristyl propyl betaine, oil Amidinopropyl betaine, olive oil guanamine propyl betaine, palm oil guanamine propyl betaine, palmitate propyl betaine, castor oil amidinopropyl betaine, sesame oil amidoxime betaine Soybean oil decyl propyl betaine, stearyl propyl betaine, tallow amidinopropyl betaine, undecylenyl propyl betaine, and wheat germ oil guanamine propyl betaine. Among these, from the viewpoint of blending stability and foaming property, it is preferably selected from the group consisting of lauric acid propyl carboxybetaine, myristyl propyl betaine, ceramide propyl betaine, and coconut. One or more of the oil guanamine propyl betaines. These compounds of the formula (I) wherein R ^3c and R ^4c are each a methyl group.

As the amine oxide, a compound of the following formula (II) is preferred.

[化10]

In the formula, R ^5c represents a hydrocarbon group having 8 or more and 22 or less carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and R ^6c and R ^7c each independently represent a carbon number of 1 or more and 3 or less. An alkyl group; D represents a -NHC(=O)- group or a -C(=O)NH- group, and E represents an alkylene group having a carbon number of 1 or more and 5 or less; m and p represent m=0 and p=0 Or m=1 and p=1]

In the above formula (II), R ^{5c is} preferably an alkyl group having 10 or more and 18 or less carbon atoms, more preferably an alkyl group having 12 or more and 16 or less carbon atoms, from the viewpoint of blending stability and foaming property. The group is more preferably an alkyl group having 12 or more and 14 or less carbon atoms, and still more preferably an alkyl group having 12 carbon atoms. From the viewpoint of the stability of the formulation, R ^6c and R ^{7c are} preferably a methyl group having a carbon number of 1.

Preferred examples of the amine oxide include (1) anthracene dimethylamine oxide, decyl dimethyl amine oxide, lauryl dimethyl amine oxide, and myristyl dimethyl amine oxide. a base (carbon number 8 or more and 22 or less) dialkyl (carbon number 1 or more and 3 or less) amine oxide, (2) lauryl propyl dimethyl amine oxide, myristyl propyl dimethyl amine oxide , a fatty acid such as palmitosylpropyl dimethylamine oxide (carbon number 8 or more and 22 or less) of amidoxime dialkyl (carbon number 1 or more and 3 or less), and from the viewpoint of the stability of the formulation, More preferably, it is (1) alkyl (carbon number 8 or more and 22 or less) dialkyl (carbon number 1 or more and 3 or less) amine oxide.

[Non-ionic surfactant] The non-ionic surfactant is preferably selected from the group consisting of (c1) monoalkyl glyceryl ether (hereinafter referred to as (c1) component from the viewpoint of blending stability and foaming property. , (c2) polyoxyalkylene monoalkyl or alkenyl ether [hereinafter referred to as (c2) component], (c3) alkylpolyglycoside (glycoside-type nonionic surfactant) [hereinafter referred to as (c3) (Component), (c4) sorbitan-based nonionic surfactant [hereinafter referred to as (c4) component], (c5) aliphatic alkanolamine (hereinafter referred to as (c5) component], (c6) fatty acid One or more of the group consisting of monoglyceride (hereinafter referred to as (c6) component) and (c7) sucrose fatty acid ester (hereinafter referred to as component (c7)) may be used in combination of two or more kinds.

The nonionic surfactant preferably contains one or more selected from the group consisting of a component (c1), a component (c2), and a component (c3), and more preferably contains a viewpoint of blending stability and foaming property. (c3) ingredients. In the nonionic surfactant, the total content of the component (c1), the component (c2), and the component (c3) is preferably 50% by mass or more, and more preferably 70, from the viewpoint of blending stability and foaming property. The mass% or more is more preferably 80% by mass or more, further preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass or less. Further, in the nonionic surfactant, the content of the component (c3) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80, from the viewpoint of blending stability and foaming property. The mass% or more is more preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 99% by mass or more, and more preferably 100% by mass or less.

The component (c1) of the component (c1) is a monoalkyl glyceryl ether. Specifically, the component (c1) is preferably a compound represented by the following formula (c1). R ^11c -O-(Gly) _r -H (c1) wherein R ^11c represents an alkyl group having 6 or more and 18 or less carbon atoms, and Gly represents a structural unit derived from glycerin, and preferably represents a hydroxyl group removed from glycerol. And a residue after one hydrogen atom, and r represents a number of 1 or more and 4 or less]

In the general formula (c1), R ^11c is preferably a carbon number of 6 or more, more preferably a carbon number of 7 or more, still more preferably a carbon number of 8 or more, from the viewpoint of foaming property and formulation stability. It is preferably an alkyl group having a carbon number of 18 or less, more preferably 12 or less carbon atoms, still more preferably 10 or less carbon atoms, and a linear alkyl group such as a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group may be used. In the present invention, from the viewpoint of the stability of the formulation, a branched alkyl group is preferred, and a specific alkyl group having a branch of R ^1c is preferred, and more preferably selected from the group consisting of 2-ethylhexyl and second octyl. The group in the isodecyl group and the isodecyl group is further preferably 2-ethylhexyl or isodecyl, more preferably 2-ethylhexyl.

In the formula (c1), r is preferably 1 or more, and preferably 2 or less. More preferably, the compound is r. More preferred compounds are those wherein R ^1c is 2-ethylhexyl and r is 1. The structure represented by Gly is a structure represented by -CH ₂ CH(OH)CH ₂ - bonded to the hydroxyl group of the 1st position and the 3 position of glycerol, or -CH which is bonded to the hydroxyl group of the 1st position and 2 position of glycerol. The structure represented by (CH ₂ OH)CH ₂ - differs depending on the catalyst or reaction conditions.

In order to obtain a compound of the formula (c1), for example, an alkyl alcohol represented by R ^11c -OH may be used as the alcohol having 6 to 10 carbon atoms, and an acid catalyst such as BF ₃ or an aluminum catalyst may be used. It is produced by reacting with an epoxy compound such as epihalohydrin or deglycerin. For example, in the case of using 2-ethylhexanol, the obtained 2-ethylhexyl monoglycerol is a mixture containing a plurality of products as described in JP-A-2001-49291.

(c2) Component (c2) The component is a polyoxyalkylene monoalkyl or alkenyl ether. In the nonionic surfactant of the component (c2), the carbon number of the alkyl group or the alkenyl group is preferably 6 or more, more preferably 8 or more, and further preferably from the viewpoint of blending stability and foaming property. It is 10 or more, and more preferably 12 or more, and from the same viewpoint, it is preferably 22 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less.

In the nonionic surfactant of the component (c2), the average addition molar number of the alkylene oxide is preferably more than 0, more preferably 1 or more, from the viewpoint of blending stability and foaming property. It is preferably 3 or more, and from the same viewpoint, it is preferably 50 or less, more preferably 30 or less, further preferably 20 or less, and still more preferably 10 or less. The alkylene oxide is preferably one or more selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and more preferably ethylene oxide, from the viewpoint of blending stability and foaming properties. And one or more of propylene oxide.

A preferred example of the nonionic surfactant as the component (c2) is a nonionic surfactant represented by the following formula (c2). R ^12c O[(C ₂ H ₄ O) _l /(C ₃ H ₆ O) _j ]H (c2) [wherein, R ^12c represents a hydrocarbon group having a carbon number of 6 or more and 22 or less; and l, j represents an average addition ratio; Molar number, l represents a number of 0 or more and 30 or less, j represents a number of 0 or more and 30 or less, and there is no case where l and j are simultaneously 0; "/" means: may be random regardless of order Adding an oxy group to an ethyl group and an oxypropyl group in any of the blocks]

The carbon number of R ^12c in the above formula (c2) is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, from the viewpoint of blending stability and foaming property, and the same viewpoint It is preferably 18 or less, more preferably 16 or less, still more preferably 14 or less. From the viewpoint of blending stability and foaming property, R ^{12c is} preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and is a second alkyl group from the viewpoint of blending stability and foaming property. Here, the term "second alkyl group" means an alkyl group in which the carbon atom of R ^12c bonded to O in the R ^12c O in the formula (c2) is a second carbon atom. Specific examples of the alkyl group include various octyl groups (including 2-ethylhexyl group), various mercapto groups, various mercapto groups, various undecyl groups, various dodecyl groups (Lauryl groups), and various tridecanes. Base, various tetradecyl groups, various pentadecyl groups, various cetyl groups, various heptadecyl groups, various octadecyl groups. Examples of the alkenyl group include various octenyl groups, various alkenyl groups, various alkenyl groups, various undecenyl groups, various dodecyl groups, various tridecenyl groups, and various tetradecenyl groups. Various pentadecenyl groups, various cetyl alkenyl groups, various heptadecenyl groups, various stearyl alkenyl groups (e.g., oleyl, linoleyl). Furthermore, the term "various" means including various isomers of positive, second, third, and different.

From the viewpoints of blending stability and foaming property, HLB (as a polyoxyalkylene monoalkyl or alkenyl ether of the component (c2), and a nonionic surfactant represented by the formula (c2) The Hydrophile Lipophile Balance (hydrophilic/oil ratio) value is preferably 5 or more, more preferably 7 or more, and from the same viewpoint, it is preferably 19 or less, more preferably 15 or less, still more preferably 13 or less. Here, the HLB value is defined by the formula of Griffin shown below. HLB value = 20 × Mw / M (wherein M is the molecular weight of the nonionic surfactant, and Mw is the molecular weight of the hydrophilic portion of the nonionic surfactant). Further, in the formula (c2), the so-called hydrophilic The sexual moiety refers to the total portion of the oxyethyl group and the oxypropyl group.

The component (c3) of the component (c3) is an alkylpolyglycoside (glycoside-type nonionic surfactant). The nonionic surfactant of the component (c3) is preferably a nonionic surfactant represented by the following formula (c3). R ^13c (OR ^14c ) _s G _t (c3) wherein R ^13c represents a linear or branched alkyl group, an alkenyl group or an alkyl group having 8 or more and 18 or less, preferably 12 or more and 14 or less carbon atoms. Phenyl group, preferably alkyl group, R ^14c represents an alkylene group having 2 or more and 4 or less carbon atoms, G represents a residue derived from a reducing sugar of 5 or 6 carbon atoms; and s represents an average addition molar number of 0. Above and below 5; t means the average value is 1 or more and 5 or less]

In the general formula (c3), R ^13c is a linear or branched having a carbon number of 8 or more, preferably 10 or more, and 18 or less, preferably 14 or less, from the viewpoint of blending stability and foaming property. Chain alkyl. In the general formula (c3), s is preferably 0 or more and 2 or less, and more preferably 0, from the viewpoint of blending stability and foaming property. From the viewpoint of blending stability and foaming property, t is preferably 1.1 or more, and is preferably 1.5 or less, more preferably 1.4 or less. Further, t is a value measured by a proton NMR (Nuclear Magnetic Resonance) method. In the general formula (c3), the residue derived from one or more monosaccharides selected from the group consisting of glucose and fructose may be mentioned as the G in terms of availability and cost. Further, examples of G include residues derived from one or more polysaccharides selected from the group consisting of maltose and sucrose. G is preferably a residue derived from a monosaccharide of glucose.

(c4) component - (c7) component (c4) sorbitan-based nonionic surfactant, (c5) aliphatic alkanolamine, (c6) fatty acid monoglyceride, and (c7) sucrose fatty acid ester It is preferably a linear or branched alkyl group having a carbon number of 8 or more and 18 or less, more preferably a carbon number of 12 or more and 14 or less.

[Anionic Surfactant] The anionic surfactant is preferably an anionic surfactant having a sulfate group, a phosphate group, a phosphonic acid group, a sulfonic acid group or a carboxyl group. The anionic surfactant has a hydrocarbyl group. The hydrocarbon group of the anionic surfactant has a carbon number of preferably 5 or more, more preferably 6 or more, still more preferably 7 or more, and still more preferably 8 from the viewpoint of blending stability and foaming property. The above is more preferably 10 or more, still more preferably 12 or more, and is preferably 21 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less. The hydrocarbon group is preferably a linear or branched alkyl group, an alkyl group or an aryl group.

The anionic surfactant is preferably selected from the group consisting of a sulfosuccinate having a hydrocarbon group having 5 or more and 18 or less carbon atoms (C8) or a salt thereof (hereinafter referred to as a component (c8)), and (c9) having a carbon number of 8 or more. And an anionic surfactant having a hydrocarbon group of 21 or less and a sulfate group or a sulfonic acid group (excluding the component (c8)] (hereinafter referred to as component (c9)) and (c10) having a carbon number of 7 or more and 21 or less An anionic surfactant (hereinafter referred to as (c10) component) of the hydrocarbon group and the carboxyl group, and (c11) an anionic surfactant having a hydrocarbon group having a carbon number of 8 or more and 21 or less and a phosphate group [hereinafter referred to as (1) The anionic surfactant of one or more of the group of the components (c11) may be used in combination of two or more kinds.

The anionic surfactant preferably contains one or more selected from the group consisting of the component (c8) and the component (c9), and more preferably contains (c9), from the viewpoint of the stability of the formulation and the foaming property. ingredient. Further, in the anionic surfactant, the content of the component (c9) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80, from the viewpoint of blending stability and foaming property. The mass% or more is more preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 99% by mass or more, and more preferably 100% by mass or less. In addition, the content (% by mass) of each component in the anionic surfactant is calculated based on the amount in terms of sodium salt.

The component (c9) used in the present invention is an anionic surfactant having a hydrocarbon group having 8 or more and 21 or less carbon atoms, and a sulfate group or a sulfonic acid group (excluding the component (c8)).

The carbon number of the hydrocarbon group of the component (c9) is 8 or more, preferably 10 or more, more preferably 12 or more, and 21 or less, preferably 18 or less, from the viewpoint of blending stability and foaming property. It is preferably 14 or less, and more preferably 12 or less. The hydrocarbon group of the component (c9) is preferably an alkyl group or an aryl group.

The anionic surfactant of the component (c9) is preferably one or more selected from the group consisting of an alkyl sulfate salt, a polyoxyalkylene alkyl sulfate salt, and an alkanesulfonate.

The anionic surfactant having a sulfate group preferably has a carbon number of 8 or more, preferably 10 or more, and 21 or less, from the viewpoint of blending stability and foaming property. A linear or branched alkyl sulfate salt of 18 or less, more preferably 14 or less, still more preferably 12 or less. Further, the anionic surfactant having a sulfate group and a polyoxyalkylene group has a carbon number of 8 or more, preferably 10 or more, and 21 from the viewpoint of blending stability and foaming property. The linear or branched alkyl group having a carbon number of 2 or more and 3 or less is preferably an average of 18 or less, more preferably 14 or less, still more preferably 12 or less. The number of moles is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.4 or more, and more preferably 6 or less, more preferably 5 or less, still more preferably 4 or less polyoxyalkylene polyoxyl Alkyl alkyl ether sulfate salt. Further, the anionic surfactant having a sulfonic acid group is preferably an alkyl group selected from the group consisting of (1) an alkyl group having 6 or more and 15 or less carbon atoms from the viewpoint of blending stability and foaming property. The benzenesulfonate and (2) the alkanesulfonate having a carbon number of 8 or more, preferably 10 or more, and 21 or less, preferably 18 or less, more preferably 14 or less, still more preferably 12 or less One or more kinds of anionic surfactants.

The salt of the anionic surfactant as the component (c9) is preferably an inorganic salt selected from the group consisting of a sodium salt, an ammonium salt, a potassium salt, a magnesium salt, and the like, and is selected from the group consisting of monoethanolammonium salt, diethanolammonium salt, and triethanol. An organic ammonium salt in an ammonium salt, a morpholinium salt or the like.

The component (c9) is preferably a compound of the following formula (c9) from the viewpoint of blending stability and foaming properties. R ^23c -O-(R ^24c O) _n -SO ₃ M ² (c9) wherein R ^23c is a linear or branched alkyl group having 8 or more and 21 or less carbon atoms, and R ^24c is an ethyl group and / or propyl, n is the average addition mole number, the number is 0 or more and 6 or less; M ² is a hydrogen atom or a cation, preferably an inorganic or organic cation]

In the general formula (c9), R ^{23c has} a carbon number of 8 or more, preferably 10 or more, 21 or less, preferably 18 or less, more preferably 14 or less, and further, from the viewpoint of the detergency. A linear or branched alkyl group of preferably 12 or less is preferably a linear alkyl group. Specifically, R ^{23c is} preferably an alkyl group selected from the group consisting of octyl, decyl, dodecyl, tridecyl, and tetradecyl, and more preferably dodecyl.

In the general formula (c9), n is preferably 0 or more, more preferably 6 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 1.5 or less from the viewpoint of foaming property. The number. Also, n can be 0. In the case of the formula (c9), when R ^24c is an ethyl group, n is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 6 or less, from the viewpoint of foaming property. It is 3 or less. Further, in the case of the formula (c9), when R ^24c is a propyl group, n is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.4 or more from the viewpoint of foaming property. Further, it is preferably 1.5 or less, more preferably 1.0 or less, still more preferably 0.8 or less. Further, in the case of the formula (c9), when R ^24c is an ethyl group and a propyl group, n can be selected from the above range for each of the groups.

In the general formula (c9), examples of the M ² include a hydrogen atom, an inorganic cation such as a sodium ion, an ammonium ion, a potassium ion or a magnesium ion, a monoethanolammonium ion, a diethanolammonium ion, a triethanolammonium ion, and a morpholinium oxime. The organic cation such as an ion is preferably an inorganic cation selected from the group consisting of sodium ion, potassium ion, ammonium ion, and magnesium ion.

In the case of obtaining a compound in which R ^23c contains a branched alkyl group in the formula (c9), the alcohol represented by R ^23c -OH as a raw material may be one having a carbon number of 8 or more and 14 or less. An alcohol obtained by subjecting an olefin to hydroformylation (including a methyl group of 15 mol% or more and 70 mol% or less of an alkyl group branched at a β position with respect to an OH group), and an aldehyde having a carbon number of 4 or more and 8 or less a gibbut type alcohol obtained by reduction after condensation (containing 100 mol% of a carbon group having 3 or more and 6 or less alkyl groups in a structure branched at a β position with respect to an OH group), and hydrogenating a dimer of isobutylene 3,5,5-trimethylhexanol obtained by formazanization, multi-branched tridecyl alcohol obtained by hydroformylating a terpolymer of isobutylene (branche rate: 100 mol%), petroleum, A synthetic alcohol having coal as a raw material (having an alkyl group having a branching ratio of about 20 mol% or more and 100 mol% or less).

The component (c10) used in the present invention is an anionic surfactant having a hydrocarbon group having 7 or more and 21 or less carbon atoms and a carboxyl group. Specific examples thereof include higher fatty acid or a salt thereof, polyoxyethylidene ether carboxylic acid or a salt thereof, N-decylamino acid or a salt thereof.

The higher fatty acid or a salt thereof is preferably represented by the following formula (c10-1). R ^25c -COOX ^1c (c10-1) wherein R ^25c represents an alkyl group or an alkenyl group having 7 or more and 21 or less carbon atoms, and X ^1c represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkanolammonium or Basic amino acid] The higher fatty acid or a salt thereof, more specifically, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, arachidic acid, behenic acid, and Such salts and the like. Among these, lauric acid, myristic acid, palmitic acid, and the like are preferred.

The polyoxyalkylene ether alkyl carboxylic acid or a salt thereof is preferably represented by the following formula (c10-2). R ^26c -O-(CH ₂ CH ₂ O) _g COOX ^2c (c10-2) wherein R ^26c represents an alkyl group or an alkenyl group having a carbon number of 7 or more, preferably 8 or more and 21 or less, and g is The average addition molar number of ethylene oxide means a number of 0.5 or more and 10 or less, and X ^2c represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium, an alkanolammonium or a basic amino acid]

In another aspect, the hard surface liquid detergent composition of the present invention is a hard surface liquid detergent composition containing the component (a), the component (b), and the component (d). Regarding the hard surface liquid detergent composition, specific examples (a), (b), and preferred aspects are as described above.

<Component (d)> The component (d) is a chelating agent. The chelating agent is preferably a compound selected from the group consisting of an aminocarboxylic acid, a hydroxycarboxylic acid, a hydroxyphosphonic acid, and one or more of these salts. The aminocarboxylic acid and a salt thereof are selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), nitrogen triacetic acid (NTA), imidodiacetic acid, diethylenetriaminepentaacetic acid (DTPA), and N. -hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), methylglycine diacetic acid (MGDA), aspartic acid diacetic acid (ASDA), glutamic acid diacetic acid (GLDA) and the salts thereof One or two or more. The aminocarboxylic acid and salts thereof are preferably one or two selected from the group consisting of ethylenediaminetetraacetic acid and salts thereof, methylglycine diacetic acid and salts thereof, and L-glutamic acid diacetic acid and salts thereof. the above. The hydroxycarboxylic acid and salts thereof are preferably compounds selected from the group consisting of aliphatic hydroxycarboxylic acids and salts thereof. Examples of the hydroxycarboxylic acid and salts thereof include compounds selected from the group consisting of malic acid, citric acid, and salts thereof. Examples of the hydroxyphosphonic acid and a salt thereof include a compound selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and a salt thereof. The salt of the chelating agent may, for example, be an alkali metal salt, an ammonium salt or an amine salt. It is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt. The chelating agent is preferably a compound selected from the group consisting of an aminocarboxylic acid, a hydroxycarboxylic acid, and a salt thereof, more preferably an aminocarboxylic acid or a salt thereof, and further preferably ethylenediaminetetraacetic acid or Its salt.

<Composition, optional component, etc.> The content of the component (a) is preferably 0.01% by mass in terms of the effect of hydrophilizing the hard surface to prevent the adhesion of the dirt in the liquid detergent composition for a hard surface of the present invention. The above is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and from the viewpoint of blending stability, it is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1 The mass% or less is more preferably 0.8% by mass or less, further preferably 0.5% by mass or less, and still more preferably 0.4% by mass or less.

Further, in the liquid detergent composition for a hard surface of the present invention, the content of the component (b) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably from the viewpoint of the sterilizing power. It is 0.1% by mass or more, and more preferably 0.2% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less, from the viewpoint of blending stability. Furthermore, it is more preferably 2% by mass or less, and still more preferably 1.5% by mass or less.

In the liquid detergent composition for a hard surface of the present invention, the quality of (a)/(b) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more from the viewpoint of preventing adhesion of dirt. Furthermore, it is more preferably 0.15 or more, and is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1 or less from the viewpoint of blending stability. . In the case where the liquid detergent composition for a hard surface of the present invention contains the component (d), the above upper limit is also preferable from the viewpoint of the sterilization performance.

Further, in the liquid detergent composition for a hard surface of the present invention containing the component (c), the content of the component (c) is preferably 0.05% by mass or more, more preferably 0.1%, from the viewpoint of foaming property. % or more, further preferably 0.15% by mass or more, and from the viewpoint of economy (low cost), it is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. More preferably, it is 3% by mass or less.

Further, when the component (c) contains an amphoteric surfactant, the liquid detergent composition for a hard surface of the present invention containing the component (c) has an amphoteric surfactant from the viewpoint of foaming property. The content is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.15% by mass or more, and from the viewpoint of economy (low cost), preferably 10% by mass or less, more preferably It is 8 mass% or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. Further, when the component (c) contains a nonionic surfactant, the liquid surface detergent composition for a hard surface of the present invention containing the component (c) is nonionic in terms of foaming property. The content of the surfactant is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and preferably 10% by mass or less from the viewpoint of economy (low cost). More preferably, it is 8% by mass or less, further preferably 5% by mass or less, and still more preferably 3% by mass or less. Further, when the component (c) contains an anionic surfactant, the liquid surfactant composition for a hard surface of the present invention containing the component (c) has an anionic interface activity from the viewpoint of foaming property. The content of the agent is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and is preferably 10% in terms of economy (low cost) and formulation stability. % or less is more preferably 8% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, and still more preferably 1% by mass or less.

Further, in the liquid detergent composition for a hard surface of the present invention containing the component (c), the quality of (b)/(c) is preferably 0.05 or more, more preferably 0.1, from the viewpoint of sterilization performance. The above is more preferably 0.15 or more, and from the viewpoint of foaming ability, it is preferably 30 or less, more preferably 25 or less, further preferably 20 or less, and still more preferably 10 or less.

Further, in the liquid detergent composition for a hard surface of the present invention containing the component (d), the content of the component (d) is preferably 0.01% by mass or more, and more preferably 0.05%, from the viewpoint of the cleaning power. % or more, further preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and preferably 10% by mass or less from the viewpoint of economy and blending stability. More preferably, it is 9% by mass or less, further preferably 8% by mass or less, more preferably 6% by mass or less, still more preferably 5% by mass or less, and still more preferably 4% by mass or less. Further, the mass of the component (d) is an acid-converted value (the same is true for other amount ratios related to the quality of the component (d)).

Further, in the liquid detergent composition for a hard surface of the present invention containing the component (d), the quality of (b)/(d) is preferably 0.01 or more, more preferably 0.03, from the viewpoint of sterilization performance. The above is more preferably 0.05 or more, further preferably 0.1 or more, and still more preferably 0.15 or more, and from the viewpoint of blending stability and detergency, it is preferably 10 or less, more preferably 5 or less. It is preferably 3 or less, more preferably 1 or less, still more preferably 0.8 or less.

The liquid detergent composition for a hard surface of the present invention containing the component (d) may contain a surfactant other than the component (b). The surfactant (c), that is, one or more selected from the group consisting of an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant, may be mentioned. From the viewpoint of the stability of the formulation, the component (c) is preferably one or more surfactants selected from the group consisting of an amphoteric surfactant and a nonionic surfactant. Specific examples and preferred aspects of the component (c) in this case are as described above. Further, in the liquid detergent composition for a hard surface of the present invention containing the component (d), the viewpoint of the fact that the component (c) is preferable is that the cleaning power can be added.

In the case where the liquid detergent composition for a hard surface of the present invention containing the component (d) contains the component (c), the content of the component (c) in the composition is preferably from the viewpoint of foaming ability. It is 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and from the viewpoint of low cost, it is preferably 10% by mass or less, more preferably 8% by mass or less, and further It is preferably 5% by mass or less, and more preferably 3% by mass or less.

Further, in the case where the liquid detergent composition for a hard surface of the present invention containing the component (d) contains an amphoteric surfactant, the content of the amphoteric surfactant in the composition is higher from the viewpoint of foaming property. The amount is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and from the viewpoint of economy (low cost), preferably 10% by mass or less, more preferably 8% by mass. % or less is further preferably 5% by mass or less, and more preferably 3% by mass or less. Further, in the case where the liquid detergent composition for a hard surface of the present invention containing the component (d) contains a nonionic surfactant, the nonionic interface activity in the composition is from the viewpoint of foaming property. The content of the agent is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.15% by mass or more, and is preferably 10% by mass or less from the viewpoint of economy (low cost). It is preferably 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. Further, in the case where the liquid detergent composition for a hard surface of the present invention containing the component (d) contains an anionic surfactant, the anionic surfactant in the composition is from the viewpoint of foaming property. The content is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.15% by mass or more, and is preferably 10% by mass or less from the viewpoint of economy (low cost) and blending stability. It is more preferably 8% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, and still more preferably 1% by mass or less.

The liquid detergent composition for hard surfaces of the present invention contains water. That is, the components (a), (b), (c), and/or (d), and the remainder other than the optional components are water. In the liquid detergent composition for a hard surface of the present invention, the water content is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and preferably 95% by mass. Hereinafter, it is more preferably 93% by mass or less. The water is preferably ion-exchanged water, sterilized ion-exchanged water or the like.

The pH of the liquid surface cleaner composition for hard surfaces of the present invention at 20 ° C is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 10 or less, more preferably 9 or less. Further, it is preferably 8 or less.

To the liquid detergent composition for hard surfaces of the present invention, polyacrylic acid, polymethacrylic acid, polymaleic acid, poly-2-propenylamine-2- can be added to the extent that the object of the present invention is not hindered a polycarboxylic acid such as methyl propanesulfonic acid or polypyrene sulfonic acid; a lower alcohol such as ethanol or isopropanol; a solvent such as diethylene glycol monobutyl ether; a tosylate, a xylene sulfonate or a urea; Solubilizing agent; viscosity modifier for clay minerals, water-soluble polymer compounds (excluding component (a)); water-insoluble grinding of calcite, vermiculite, calcium phosphate, zeolite, calcium carbonate, polyethylene, nylon, polystyrene, etc. Agent; humectant such as glycerin or sorbitol; touch enhancer such as cationized cellulose (excluding component (a)); alkaline adjuvant such as sodium carbonate and sodium citrate; enzyme, pigment, fragrance, antiseptic, Mold inhibitors, etc.

[Method for preventing adhesion of dirt on hard surface] The present invention relates to a method for preventing adhesion of dirt on a hard surface by treating the hard surface with the above-described liquid detergent composition for a hard surface of the present invention.

The hard surface is not particularly limited, and examples thereof include glass, ceramics, magnets, crucibles, tiles, ceramics; metals such as aluminum, stainless steel, and brass; polyethylene, polypropylene, melamine resin, polyamide resin, and ABS (acrylonitrile- Butadiene-styrene, acrylonitrile-butadiene-styrene resin, synthetic resin such as FRP (fiber reinforced plastics); natural fibers such as cotton, silk and wool; synthetic fibers such as polyester, nylon and enamel Solid hard surface. The fiber is preferably a fiber product having a shape or strength suitable for the treatment with the liquid detergent composition for a hard surface of the present invention. As the hard surface to which the composition and treatment method of the present invention can be applied, a hydrophilic hard surface is preferred. Here, the term "hydrophilic" with respect to a hard surface means that the static contact angle with respect to water is less than 70°. Further, the static contact angle can be measured by the method described in the examples. The hard surface which is preferable in the invention may be one or more hard surfaces selected from the group consisting of glass, ceramics, magnets, plastics, stainless steel, and tantalum wafers.

The object of the invention is a hard surface, in particular an article having a hard surface. Examples of the article having a hard surface include a toilet, a bathtub, a kitchen sink, a window glass, a mirror, a faucet, and the like.

In the method for preventing adhesion of dirt according to the present invention, it is preferred to use a liquid for washing a hard surface of the present invention containing the component (a), the component (b), and the component (c) and/or the component (d) in the above-mentioned content. Detergent composition.

The treatment of the hard surface by the liquid surface cleaner composition for hard surfaces of the present invention can be carried out by bringing the hard surface liquid detergent composition of the present invention into contact with a hard surface. The method of contacting the hard surface liquid detergent composition of the present invention with a hard surface is not particularly limited. For example, the following methods (i) to (ii) can be mentioned. (i) a method of immersing an article having a hard surface in the liquid detergent composition for a hard surface of the present invention (ii) a method of spraying or coating a hard surface liquid detergent composition of the present invention on a hard surface

In the method of the above (i), the immersion time is preferably 0.5 minutes or more, more preferably 1 minute or more, and preferably 60 minutes or less, from the viewpoint of improving the antifouling performance and economy. It is 50 minutes or less. In the method of the above (ii), the method of spraying or applying the hard surface liquid detergent composition of the present invention to the hard surface can be appropriately selected depending on the width (area) of the hard surface or the like. Preferably, the hard surface liquid detergent composition of the present invention is sprayed onto a hard surface by a spray or the like, followed by drying. It can also be rinsed with water after spraying as needed. Moreover, it can also be spread thinly after spraying, using a sponge or the like. Alternatively, the hard surface liquid detergent composition of the present invention may be directly applied by discharging it from a discharge container such as a plastic bottle to a hard surface. The amount of the liquid surface cleaner composition for hard surfaces of the present invention which is sprayed or applied to a hard surface is, for example, preferably 0.01 mL or more and 1 mL or less, more preferably 0.01 mL or more and 0.1 mL or less per 10 cm ² .

The temperature of the hard surface liquid detergent composition of the present invention which is treated on a hard surface is preferably 5 ° C or higher, more preferably 10 ° C, from the viewpoint of improving the antifouling performance and the easiness of the treatment method. The above is more preferably 15 ° C or higher, and is preferably 50 ° C or lower, more preferably 40 ° C or lower, and still more preferably 30 ° C or lower.

Further, from the viewpoint of imparting hydrophilicity to the hard surface and improving the antifouling property, the hard surface treated with the liquid surface cleaner composition for a hard surface of the present invention is preferably a hydrophilic hard surface, more preferably a glass. The static contact angle of the surface to water is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, still more preferably 8 or less, and more preferably 1 or more. By imparting hydrophilicity to the hard surface in this manner, the antifouling property of the hard surface against the hydrophobic substance can be improved. The static contact angle of the glass surface with respect to water can be determined by the method described in the examples. Further, from the viewpoint of improving the antifouling performance and the like, the hard surface treated by the liquid surface cleaner composition for hard surfaces of the present invention is preferably uniformly treated. The uniformity of the surface treatment can be judged by visually observing the treated hard surface. Further, when the hard surface is a toilet, it may be used by dissolving the hard surface liquid detergent composition of the present invention in the washing water in the water tank to continuously wash the dirt of the toilet. In this case, a certain amount can be dropped into the toilet tank automatically or manually.

<Section of the Present Invention> The aspect of the present invention is exemplified below. In the above-described aspect, the matters described in the method for preventing the adhesion of dirt and the liquid detergent composition of the present invention can be suitably applied.

<1a> A liquid detergent composition for a hard surface, comprising: (a) a structural unit (a1) represented by the following formula (1); and a structural unit represented by the following formula (2) (a2) And the molar ratio of the structural unit (a1) to the structural unit (a2), that is, the structural unit (a1)/structural unit (a2) is a copolymer of 30/70 or more and 99.9/0.1 or less [hereinafter referred to as (a) component And (b) a cationic surfactant (hereinafter referred to as component (b)), and (c) one or more interface activities selected from the group consisting of an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant Agent [hereinafter referred to as component (c)].

[11]

Wherein R ¹ to R ^{3 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; and R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, or -Y ¹ -OPO ₃ ^- - Y ² -, Y ¹ and Y ^{2 are the} same or different and are an alkylene group having 1 or more and 4 or less carbon atoms, and R ⁵ and R ^{6 are the} same or different, and are a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ¹ is O. Or NR ⁷ , R ⁷ is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ² represents a hydrogen atom, a hydrocarbon group having 1 or more and 4 or less carbon atoms, R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- ; When R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, X ² is R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- , and R ¹⁷ is an alkylene group having 1 or more and 4 or less carbon atoms, and is R ^{4 .} When -Y ¹ -OPO ₃ ^- -Y ² -, X ² is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms]

[化12]

Wherein R ⁸ to R ^{10 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; X ³ is O; R ¹¹ is an alkylene group having 1 or more and 4 or less carbon atoms, and X ⁴ is N. ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ , and R ¹² to R ^{16 are the} same or different and each represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ⁵ represents an anion]

<2a> The liquid surface cleaner composition for hard surfaces according to <1a>, wherein the weight average molecular weight of the component (a) is preferably 500 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and furthermore Preferably, it is 30,000 or more, and is preferably 200,000 or less, more preferably 150,000 or less, and further preferably 100,000 or less.

<3a> The liquid surface cleaner composition for hard surfaces according to <1a> or <2a>, wherein the molar ratio of the structural unit (a1) of the component (a) to the structural unit (a2) is a structural unit (a1) The structural unit (a2) is preferably 30/70 or more, preferably 50/50 or more, more preferably 55/45 or more, further preferably 60/40 or more, and still more preferably 75/25 or more, and further preferably It is 90/10 or more, and is 99.9/0.1 or less, preferably 98/2 or less, more preferably 96/4 or less.

The hard surface liquid detergent composition according to any one of the above-mentioned, wherein the content of the structural unit (a1) in the component (a) is preferably 30 mol% or more. More preferably, it is 50 mol% or more, further preferably 70 mol% or more, further preferably 80 mol% or more, further preferably 90 mol% or more, and preferably 99 mol% or less, more preferably Preferably, it is 98% or less, more preferably 95% by mole or less.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the content of the structural unit (a2) in the component (a) is preferably 1 mol% or more. More preferably, it is 2 mol% or more, further preferably 5 mol% or more, and preferably 70 mol% or less, more preferably 50 mol% or less, further preferably 30 mol% or less, and further preferably It is preferably 20 mol% or less, more preferably 10 mol% or less.

The hard surface liquid detergent composition of any one of the components (a1) and the structural unit other than the structural unit (a2) in the component (a). The content is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 1 mol% or less, further preferably 0.5 mol% or less, further preferably 0.1 mol% or less, or 0 mole %.

The liquid detergent composition for hard surfaces according to any one of <1a> to <6a>, wherein the total content of the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 90 mol% or more, more preferably 95 mol% or more, further preferably 99 mol% or more, further preferably 99.5 mol% or more, further preferably 99.9 mol% or more, or 100 mol ear%.

The liquid detergent composition for hard surfaces according to any one of <1a> to <7a> wherein the component (b) is a cation selected from a mono- or di-long-chain alkyl type quaternary ammonium salt. Sexual surfactant.

The hard surface liquid detergent composition according to any one of the above-mentioned items (b), wherein the component (b) is a compound selected from the group consisting of the following formula (b1) and a formula ( B2) a cationic surfactant in the compound represented.

[Chemistry 13]

In the formula, at least one selected from the group consisting of R ^1b and R ^2b represents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 or more and 18 or less carbon atoms, and the others represent an alkyl group having 1 to 3 or less carbon atoms and a hydroxyalkane group. a base or an average addition of a polyoxyl group having a molar number of 10 or less, and R ^3b and R ^{4b are the} same or different, and each represents an alkyl group having a carbon number of 1 or more and 3 or less, a hydroxyalkyl group or an average addition mole number of 10 The following polyoxyalkylene group, Y ^- represents a halogen atom, or an anion residue of a sulfonate or sulfate having a carbon number of 1 or more and 5 or less]

[Chemistry 14]

In the formula, R ^5b represents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 or more and 18 or less carbon atoms, and R ^6b and R ^{7b are the} same or different and each represents an alkyl group having 1 to 3 or more carbon atoms and a hydroxyalkyl group. Or an average addition of a polyoxyalkylene group having a molar number of 10 or less, R ^8b represents an alkylene group having a carbon number of 1 or more and 3 or less; Z ^- represents a halogen atom, or a sulfonic acid ester having a carbon number of 1 or more and 5 or less or Sulfate anion residue]

The hard surface liquid detergent composition according to any one of the above-mentioned, wherein the component (c) is one or more selected from the group consisting of an amphoteric surfactant and a nonionic surfactant. Surfactant.

The liquid detergent composition for hard surfaces according to any one of <1a> to <10a> wherein the amphoteric surfactant is one selected from the group consisting of amine oxides, sulfobetaines, and carboxybetaines. The above amphoteric surfactant is preferably one or more kinds of amphoteric surfactants selected from the group consisting of sulfobetaine and carboxybetaine, and more preferably carboxybetaine.

The liquid detergent composition for hard surfaces according to any one of <1a> to <11, wherein the amphoteric surfactant is one selected from the group consisting of amine oxides, sulfobetaines, and carboxybetaines. The content of the above-mentioned amphoteric surfactant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more. Further, it is more preferably 99% by mass or more, and is preferably 100% by mass or less.

The liquid detergent composition for a hard surface according to any one of the above-mentioned, wherein the amphoteric surfactant is one or more selected from the group consisting of sulfobetaine and carboxybetaine. The content of the surfactant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and furthermore It is preferably 99% by mass or more, and preferably 100% by mass or less.

The liquid detergent composition for hard surfaces according to any one of <1a> to <13a>, wherein the nonionic surfactant is selected from (c1) monoalkyl glyceryl ether [hereinafter referred to as ( C1) component], (c2) polyoxyalkylene monoalkyl or alkenyl ether [hereinafter referred to as (c2) component], (c3) alkylpolyglycoside (glycoside-type nonionic surfactant) [hereinafter referred to as (c3) component], (c4) sorbitan-based nonionic surfactant [hereinafter referred to as (c4) component], (c5) aliphatic alkanolamine (hereinafter referred to as (c5) component], ( C6) One or more kinds of nonionic surfactants in a group consisting of fatty acid monoglyceride (hereinafter referred to as (c6) component] and (c7) sucrose fatty acid ester (hereinafter referred to as component (c7)).

The liquid detergent composition for a hard surface according to <14a>, wherein the nonionic surfactant is one or more selected from the group consisting of a component (c1), a component (c2), and a component (c3). The ionic surfactant is preferably a component (c3).

<16a> The liquid surface cleaner composition for hard surfaces according to <14a> or <15a>, wherein the content of the component (c3) in the nonionic surfactant is preferably 50% by mass or more, more preferably 70% by mass. % or more is further preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass or less.

The liquid detergent composition for a hard surface according to any one of <1a> to <16, wherein the anionic surfactant has a sulfate group, a phosphate group, a phosphonic acid group, or a sulfonic acid group. Or an anionic surfactant of a carboxyl group.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the anionic surfactant has a hydrocarbon group, and the carbon number of the hydrocarbon group is preferably 5 or more, more preferably 6 or more, more preferably 7 or more, still more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, and most preferably 21 or less, more preferably 18 or less, still more preferably 16 or less. More preferably, it is 14 or less, and the hydrocarbon group is a linear or branched alkyl group, an alkyl group or an aryl group.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the anionic surfactant is selected from the group consisting of a hydrocarbon group having a carbon number of 5 or more and 18 or less (c8). Sulfosuccinate or a salt thereof (hereinafter referred to as (c8) component], (c9) an anionic surfactant having a hydrocarbon group of 8 or more and 21 or less, and a sulfate group or a sulfonic acid group [where (c9) component (hereinafter referred to as (c9) component), (c10) an alkoxy surfactant having a carbon number of 7 or more and 21 or less, and an anionic surfactant (hereinafter referred to as a component (c10)), and (c11) An anionic surfactant having one or more of a group consisting of a hydrocarbon group having 8 or more and 21 or less carbon atoms and an anionic surfactant (hereinafter referred to as a component (c11)) having a phosphate group.

The liquid detergent composition for a hard surface according to <19a>, wherein the anionic surfactant is one or more anionic interfaces selected from the group consisting of the component (c8) and the component (c9). The active agent is preferably one or more anionic surfactants selected from the group consisting of (c9).

The liquid detergent composition for a hard surface according to <19a> or <20a>, wherein the content of the component (c9) in the anionic surfactant is preferably 50% by mass or more, more preferably 70% by mass. The above is more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass or less.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the content of the component (a) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Further, it is preferably 0.1% by mass or more, more preferably 3% by mass or less, still more preferably 2% by mass or less, still more preferably 1% by mass or less, still more preferably 0.8% by mass or less, and still more preferably 0.5% by mass. % or less, more preferably 0.4% by mass or less.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the content of the component (b) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Further, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, and still more preferably 2% by mass. % or less, more preferably 1.5% by mass or less.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the content of the component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more. Further, it is preferably 0.15% by mass or more, more preferably 10% by mass or less, still more preferably 8% by mass or less, further preferably 5% by mass or less, and still more preferably 3% by mass or less.

The liquid detergent composition for a hard surface according to any one of <1a> to <24a>, wherein the mass of (a)/(b) is preferably 0.01 or more, more preferably 0.05 or more, and further It is preferably 0.1 or more, more preferably 0.15 or more, and is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1 or less.

The hard surface liquid detergent composition according to any one of <1a> to <25a>, wherein the mass of (b)/(c) is preferably 0.05 or more, more preferably 0.1 or more, and further It is preferably 0.15 or more, and is preferably 30 or less, more preferably 25 or less, further preferably 20 or less, and still more preferably 10 or less.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the water content is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably It is 60% by mass or more, and preferably 95% by mass or less, more preferably 93% by mass or less.

The hard surface liquid detergent composition according to any one of <1a> to <27a>, wherein the hard surface is a hydrophilic hard surface.

The hard surface liquid detergent composition according to any one of the above aspects, wherein the hard surface surface treated with the hard surface liquid detergent composition is preferably a hydrophilic hard surface. The surface, more preferably the surface contact angle of the glass surface with respect to water is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and still more preferably 8 or less.

<30a> A method for preventing the adhesion of the hard surface to the hard surface. The hard surface is treated with the liquid detergent composition for a hard surface according to any one of <1a> to <29a>.

<31a> A method for preventing adhesion of dirt on a hard surface as described in <30a>, wherein the hard surface is a hydrophilic hard surface.

<32a> A method for preventing adhesion of dirt on a hard surface as described in <30a> or <31a>, wherein the hard surface is: glass, ceramics, magnets, crucibles, tiles, ceramics; metals such as aluminum, stainless steel, brass; , polypropylene, melamine resin, polyamide resin, ABS resin, FRP and other synthetic resins; cotton, silk, wool and other natural fibers; polyester, nylon, enamel and other synthetic fibers and other solid hard surface.

<33a> The method for preventing adhesion of dirt on a hard surface according to any one of <30a> to <32a>, wherein the hard surface is one or two selected from the group consisting of glass, ceramics, magnets, plastics, stainless steel, and tantalum wafers. More than one hard surface.

<34a> The method for preventing adhesion of dirt on a hard surface according to any one of <30a> to <33a>, wherein the article having a hard surface is further selected from the group consisting of a toilet, a bathtub, a kitchen sink, a window glass, a mirror, and a faucet Items with a hard surface are processed.

The method for preventing adhesion of dirt on a hard surface according to any one of <30a> to <34a>, wherein the hard surface treated with the liquid detergent composition for a hard surface, preferably a hydrophilic hard surface, More preferably, the static contact angle of the glass surface to water is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and still more preferably 8 or less.

<36a> The use of the composition according to any one of <1a> to <29a> as a liquid detergent for a hard surface.

<1b> A liquid detergent composition for a hard surface, comprising: (a) a structural unit (a1) represented by the following formula (1); and a structural unit represented by the following formula (2) (a2) And the molar ratio of the structural unit (a1) to the structural unit (a2), that is, the structural unit (a1)/structural unit (a2) is a copolymer of 30/70 or more and 99.9/0.1 or less [hereinafter referred to as (a) component And (b) a cationic surfactant (hereinafter referred to as component (b)) and (d) a chelating agent (hereinafter referred to as component (d)).

[化15]

Wherein R ¹ to R ^{3 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; and R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, or -Y ¹ -OPO ₃ ^- - Y ² -, Y ¹ and Y ^{2 are the} same or different and are an alkylene group having 1 or more and 4 or less carbon atoms, and R ⁵ and R ^{6 are the} same or different, and are a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ¹ is O. Or NR ⁷ , R ⁷ is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ² represents a hydrogen atom, a hydrocarbon group having 1 or more and 4 or less carbon atoms, R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- ; When R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, X ² is R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- , and R ¹⁷ is an alkylene group having 1 or more and 4 or less carbon atoms, and is R ^{4 .} When -Y ¹ -OPO ₃ ^- -Y ² -, X ² is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms]

[Chemistry 16]

Wherein R ⁸ to R ^{10 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; X ³ is O; R ¹¹ is an alkylene group having 1 or more and 4 or less carbon atoms, and X ⁴ is N. ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ , and R ¹² to R ^{16 are the} same or different and each represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ⁵ represents an anion]

<2b> The liquid surface cleaner composition for hard surfaces according to <1b>, wherein the weight average molecular weight of the component (a) is preferably 500 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and furthermore Preferably, it is 30,000 or more, and is preferably 200,000 or less, more preferably 150,000 or less, and further preferably 100,000 or less.

<3b> The liquid surface cleaner composition for hard surfaces according to <1b> or <2b>, wherein the structural unit (a1) of the component (a) and the structural unit (a2) are structural units (a1) The structural unit (a2) is preferably 30/70 or more, preferably 50/50 or more, more preferably 55/45 or more, further preferably 60/40 or more, and still more preferably 75/25 or more, and further preferably It is 90/10 or more, and is 99.9/0.1 or less, preferably 98/2 or less, more preferably 96/4 or less.

The hard surface liquid detergent composition according to any one of the above-mentioned, wherein the content of the structural unit (a1) in the component (a) is preferably 30 mol% or more. More preferably, it is 50 mol% or more, further preferably 70 mol% or more, further preferably 80 mol% or more, further preferably 90 mol% or more, and preferably 99 mol% or less, more preferably Preferably, it is 98% or less, more preferably 95% by mole or less.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the content of the structural unit (a2) in the component (a) is preferably 1 mol% or more. More preferably, it is 2 mol% or more, further preferably 5 mol% or more, and preferably 70 mol% or less, more preferably 50 mol% or less, further preferably 30 mol% or less, and further preferably It is preferably 20 mol% or less, more preferably 10 mol% or less.

The hard surface liquid detergent composition according to any one of the above-mentioned, wherein the structural unit (a1) and the structural unit (a2) in the component (a) are The content is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 1 mol% or less, further preferably 0.5 mol% or less, further preferably 0.1 mol% or less, or 0 mole %.

The liquid detergent composition for a hard surface according to any one of <1b> to <6b>, wherein the total content of the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 90 mol% or more, more preferably 95 mol% or more, further preferably 99 mol% or more, further preferably 99.5 mol% or more, further preferably 99.9 mol% or more, or 100 mol ear%.

The hard surface liquid detergent composition according to any one of <1b> to <7b> wherein the component (b) is a mono- or di-long-chain alkyl type quaternary ammonium salt.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the component (b) is a compound selected from the group consisting of the following formula (b1) and a formula ( B2) a cationic surfactant in the compound represented.

[化17]

In the formula, at least one selected from the group consisting of R ^1b and R ^2b represents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 or more and 18 or less carbon atoms, and the others represent an alkyl group having 1 to 3 or less carbon atoms and a hydroxyalkane group. a base or an average addition of a polyoxyl group having a molar number of 10 or less, and R ^3b and R ^{4b are the} same or different, and each represents an alkyl group having a carbon number of 1 or more and 3 or less, a hydroxyalkyl group or an average addition mole number of 10 The following polyoxyalkylene group, Y ^- represents a halogen atom, or an anion residue of a sulfonate or sulfate having a carbon number of 1 or more and 5 or less]

[化18]

In the formula, R ^5b represents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 or more and 18 or less carbon atoms, and R ^6b and R ^{7b are the} same or different and each represents an alkyl group having 1 to 3 or more carbon atoms and a hydroxyalkyl group. Or an average addition of a polyoxyalkylene group having a molar number of 10 or less, R ^8b represents an alkylene group having a carbon number of 1 or more and 3 or less; Z ^- represents a halogen atom, or a sulfonic acid ester having a carbon number of 1 or more and 5 or less or Sulfate anion residue]

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the component (d) is selected from the group consisting of an aminocarboxylic acid, a hydroxycarboxylic acid, a hydroxyphosphonic acid, and the like. One or more compounds of the salt.

The hard surface liquid detergent composition according to any one of <1b> to <10b> wherein the component (d) is selected from the group consisting of aminocarboxylic acids, hydroxycarboxylic acids, and the like. The compound of one or more kinds is preferably an aminocarboxylic acid or a salt thereof, more preferably ethylenediaminetetraacetic acid or a salt thereof.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the content of the component (a) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Further, it is preferably 0.1% by mass or more, more preferably 3% by mass or less, still more preferably 2% by mass or less, still more preferably 1% by mass or less, still more preferably 0.8% by mass or less, and still more preferably 0.5% by mass. % or less, more preferably 0.4% by mass or less.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the content of the component (b) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Further, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, and still more preferably 2% by mass. % or less is more preferably 1.5% by mass or less, and still more preferably 1% by mass or less.

The liquid detergent composition for a hard surface according to any one of the above aspects, wherein the content of the component (d) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Further, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and is preferably 10% by mass or less, more preferably 9% by mass or less, and still more preferably 8% by mass. % or less is more preferably 6% by mass or less, still more preferably 5% by mass or less, and still more preferably 4% by mass or less.

The liquid detergent composition for hard surfaces according to any one of <1b> to <14b>, wherein the mass of (a)/(b) is preferably 0.01 or more, more preferably 0.05 or more, and further It is preferably 0.1 or more, more preferably 0.15 or more, and is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1 or less.

The hard surface liquid detergent composition according to any one of the above-mentioned, wherein the mass ratio of (b) / (d) is 0.01 or more, more preferably 0.03 or more, and further It is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.15 or more, and is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, still more preferably 1 or less, and still more preferably 0.8 or less.

The hard surface liquid detergent composition according to any one of <1> to <16b>, which contains a surfactant other than the component (b) (hereinafter referred to as component (c)).

<18b> The liquid surface cleaner composition for hard surfaces according to <17b>, wherein the component (c) is one or more selected from the group consisting of an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant. The active agent is preferably one or more selected from the group consisting of an amphoteric surfactant and a nonionic surfactant.

<19b> The liquid surface cleaner composition for hard surfaces according to <18b>, wherein the amphoteric surfactant is one or more kinds of amphoteric surfactants selected from the group consisting of amine oxides, sulfobetaines, and carboxybetaines. It is preferably one or more kinds of amphoteric surfactants selected from the group consisting of sulfobetaine and carboxybetaine.

<20b> The liquid surface cleaner composition for hard surfaces according to <18b> or <19b>, wherein the nonionic surfactant is selected from (c1) monoalkyl glyceryl ether, (c2) polyoxyalkylene alkyl group a monoalkyl or alkenyl ether, (c3) alkyl polyglycoside (glycoside-type nonionic surfactant), (c4) a sorbitan-based nonionic surfactant, (c5) an aliphatic alkanolamine, (c6) One or more kinds of nonionic surfactants in a group consisting of a fatty acid monoglyceride and (c7) a sucrose fatty acid ester.

The liquid detergent composition for a hard surface according to any one of the above-mentioned, wherein the anionic surfactant is selected from the group consisting of a hydrocarbon group having a carbon number of 5 or more and 18 or less (c8). a sulfosuccinate or a salt thereof, (c9) an anionic surfactant having a hydrocarbon group of 8 or more and 21 or less, and a sulfate group or a sulfonic acid group (excluding (c8)] and (c10) An anionic surfactant having a hydrocarbon group of 7 or more and 21 or less and an anionic surfactant having a carboxyl group; and (c11) an anionic surfactant having a hydrocarbon group having 8 or more and 21 or less and a phosphate group; One or more kinds of anionic surfactants.

The liquid detergent composition for a hard surface according to any one of the above-mentioned, wherein the content of the component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more. Further, it is preferably 0.15% by mass or more, more preferably 10% by mass or less, still more preferably 8% by mass or less, further preferably 5% by mass or less, and still more preferably 3% by mass or less.

The hard surface liquid detergent composition according to any one of the above aspects, wherein the water content is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably It is 60% by mass or more, and preferably 95% by mass or less, more preferably 93% by mass or less.

The hard surface liquid detergent composition according to any one of <1b> to <23b> wherein the hard surface is a hydrophilic hard surface.

<25b> A method for preventing the adhesion of the hard surface to the hard surface, wherein the hard surface is treated with the liquid detergent composition for a hard surface according to any one of <1b> to <24b>.

<26b> A method for preventing adhesion of dirt on a hard surface as described in <25b>, wherein the hard surface is a hydrophilic hard surface.

<27b> A method for preventing adhesion of dirt on a hard surface as described in <25b> or <26b>, wherein the hard surface is: glass, ceramics, magnets, crucibles, tiles, ceramics; metals such as aluminum, stainless steel, brass; , polypropylene, melamine resin, polyamide resin, ABS resin, FRP and other synthetic resins; cotton, silk, wool and other natural fibers; polyester, nylon, enamel and other synthetic fibers and other solid hard surface.

<28b> The method for preventing adhesion of dirt on a hard surface according to any one of <25b> to <27b>, wherein the hard surface is one or two selected from the group consisting of glass, ceramics, magnets, plastics, stainless steel, and tantalum wafers. More than one hard surface.

<29b> The method for preventing adhesion of dirt on a hard surface according to any one of <25b> to <28b>, wherein the article having a hard surface is further selected from the group consisting of a toilet, a bathtub, a kitchen sink, a window glass, a mirror, and a faucet Items with a hard surface are processed.

The method for preventing adhesion of dirt on a hard surface according to any one of <25b> to <29b>, wherein a hard surface, preferably a hydrophilic hard surface, is treated with a liquid detergent composition for a hard surface, More preferably, the static contact angle of the glass surface to water is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, still more preferably 8 or less, and more preferably 1 or more.

<31b> The use of the composition according to any one of <1b> to <24b> as a liquid detergent for a hard surface.

Example Production Example 1 [Production of Copolymer A1] (Step 1) To a four-necked flask having a volume of 1000 mL, 126.30 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was placed, and the temperature was raised to 78 ° C to reflux. 2-(dimethylamino)ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 181.12 g, 2-(dimethylamino)ethyl methacrylate diethyl ether was added dropwise thereto over 2 hours. a solution of a mixture of 23.60 g of ethanol and a mixture of 53.20 g of ethanol, and 2,2'-azobis(2-methylbutyronitrile) (Wako Pure Chemical Industries, Ltd.) The company) manufactures a solution of 5.83 g and 10.00 g of ethanol. After aging for 4 hours, it was cooled to obtain a polymer solution.

(Step 2) 94.70 g of the obtained polymer solution, 3.15 g of sodium hydrogencarbonate (manufactured by Wako Pure Chemical Industries, Ltd.), and 150.00 g of water were added to a four-necked flask having a volume of 1000 mL, and the temperature was raised to 50 °C. The reaction was carried out by dropwise addition of 38.70 g of 1,3-propane sultone (manufactured by Tokyo Chemical Industry Co., Ltd.) over 1 hour. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C / 20 kPa for 2 hours to obtain an aqueous solution containing the copolymer A1.

In the copolymer A1, the structural unit (a1) has the following structure in the formula (1), and the structural unit (a2) has the following structure in the formula (2), and the molar ratio of the structural unit (a1) / structural unit (a2) For 95/5. Structural unit (a1): R ¹ = R ² = H, R ³ = CH ₃ , R ⁴ = C ₂ H ₄ , R ⁵ = R ⁶ = CH ₃ , X ¹ = O, X ² = R ¹⁷ SO ₃ ^- , R ¹⁷ =C ₃ H ₆ structural unit (a2): R ⁸ =R ⁹ =H, R ¹⁰ =CH ₃ , X ³ =O, R ¹¹ =C ₂ H ₄ , X ⁴ =N ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ , R ¹² = R ¹³ = CH ₃ , R ¹⁴ = C ₂ H ₅ , X ⁵ = C ₂ H ₅ SO ₄ ^- Further, the weight average molecular weight of the copolymer A1 is 63,000.

Production Example 2 [Production of Copolymer A2] (Step 1) 37.95 g of ethanol was placed in a four-necked flask having a volume of 1000 mL, and the temperature was raised to 78 ° C to reflux. Mixing 122.94 g of 2-(dimethylamino)ethyl methacrylate, 30.06 g of 2-(dimethylamino)ethyl methacrylate, and 28.88 g of ethanol were added dropwise thereto over 2 hours. The resulting solution and a solution obtained by mixing 2,2'-azobis(2-methylbutyronitrile) 1.67 g and ethanol 3.90 g were polymerized. After aging for 4 hours, it was cooled to obtain a polymer solution. (Step 2) To a four-necked flask having a volume of 1000 mL, 230.77 g of the obtained polymer solution, 6.56 g of sodium hydrogencarbonate, and 308.91 g of water were added and the temperature was raised to 50 °C. The reaction was carried out by dropwise adding 102.21 g of 1,3-propane sultone to the mixture over 1 hour. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C / 20 kPa for 2 hours to obtain an aqueous polymer solution containing copolymer A2.

In the copolymer A2, the structural units (a1) and (a2) are the same as the copolymer A1, and the molar ratio of the structural unit (a1)/structural unit (a2) is 90/10. Further, the weight average molecular weight of the copolymer A2 was 69,000.

Production Example 3 [Production of Copolymer A3] (Step 1) 94.46 g of ethanol was placed in a four-necked flask having a volume of 1000 mL, and the temperature was raised to 78 ° C to reflux. Mixing 267.52 g of 2-(dimethylamino)ethyl methacrylate, 147.20 g of 2-(dimethylamino)ethyl methacrylate, and 78.29 g of ethanol were added dropwise thereto over 2 hours. The resulting solution and a solution obtained by mixing 2,2'-azobis(2-methylbutyronitrile) 4.09 g and ethanol 9.54 g were polymerized. After aging for 4 hours, it was cooled to obtain a polymer solution. (Step 2) To a four-necked flask having a volume of 1000 mL, 307.82 g of the obtained polymer solution, 7.15 g of sodium hydrogencarbonate, and 394.56 g of water were added and the temperature was raised to 50 °C. The reaction was carried out by dropwise adding 111.20 g of 1,3-propane sultone to the mixture over 1 hour. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C / 20 kPa for 2 hours to obtain an aqueous polymer solution containing copolymer A3.

In the copolymer A3, the structural units (a1) and (a2) are the same as the copolymer A1, and the molar ratio of the structural unit (a1)/structural unit (a2) is 80/20. Further, the weight average molecular weight of the copolymer A3 was 78,000.

Production Example 4 [Production of Copolymer A4] (Step 1) 33.27 g of ethanol was placed in a four-necked flask having a volume of 1000 mL, and the mixture was heated to 78 ° C to reflux. Mixing 81.13 g of 2-(dimethylamino)ethyl methacrylate, 76.52 g of 2-(dimethylamino)ethyl methacrylate, and 29.76 g of ethanol were added dropwise thereto over 2 hours. The resulting solution and a solution obtained by mixing 2,2'-azobis(2-methylbutyronitrile) 1.42 g and 3.31 g of ethanol were polymerized. After aging for 4 hours, it was cooled to obtain a polymer solution. (Step 2) 230.77 g of the obtained polymer solution, 4.34 g of sodium hydrogencarbonate, and 285.67 g of water were added to a four-necked flask having a volume of 1000 mL, and the temperature was raised to 50 °C. The reaction was carried out by dropwise adding 67.45 g of 1,3-propane sultone to the mixture over 1 hour. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C / 20 kPa for 2 hours to obtain a polymer aqueous solution containing a copolymer.

In the copolymer A4, the structural units (a1) and (a2) are the same as the copolymer A1, and the molar ratio of the structural unit (a1)/structural unit (a2) is 70/30. Further, the weight average molecular weight of the copolymer A4 was 81,000.

Production Example 5 [Production of Polymer A'1] (Step 1) 53.23 g of ethanol was placed in a four-necked flask having a 500 mL content, and the temperature was raised to 78 ° C to reflux. A solution of 150.00 g of 2-(dimethylamino)ethyl methacrylate and 16.60 g of ethanol was added dropwise thereto over 2 hours, and 2,2'-azobis(2-methylbutyl) was added thereto. Polymerization was carried out by mixing a solution of 0.92 g of nitrile and 10.00 g of ethanol. After aging for 4 hours, it was cooled to obtain a polymer solution. (Step 2) 75.76 g of the obtained polymer solution, 3.47 g of sodium hydrogencarbonate, 150.00 g of water were added to a four-necked flask having a volume of 1000 mL, and the temperature was raised to 50 °C. The reaction was carried out by dropwise adding 42.73 g of 1,3-propane sultone to the mixture over 1 hour. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C / 20 kPa for 2 hours to obtain an aqueous polymer solution containing the polymer A'1.

The polymer A'1 is a polymer containing only the structural unit (a1) which is the same as the copolymer A1 as a structural unit (the structural unit (a1) is 100 mol%). Further, the weight average molecular weight of the polymer A'1 was 40,000.

Further, the weight average molecular weight of the copolymers A1 to A4 was measured by gel permeation chromatography (amylopectin) under the following conditions. Pipe string: Two TSKgel α-M (manufactured by Tosoh) are used in series. Column temperature: 40 ° C Eluent: 0.15 mol Na ₂ SO ₄ /1% CH ₃ COOH / water flow: 1.0 ml / min Detector: differential refractometer

Further, the weight average molecular weight of the polymer A'1 was measured by SLS (Static Light Scattering). In other words, static light scattering was measured by the following conditions using a light scattering photometer "DLS-7000" (manufactured by Otsuka Electronics Co., Ltd.), and Zimm-plot was produced and calculated. Further, the refractive index increment required for the calculation of the molecular weight was measured using a differential refractometer "DRM3000" (manufactured by Otsuka Electronics Co., Ltd.). Wavelength: 632.8 nm (氦-氖 laser) Scattering angle: measured every 10° from 30° to 150°. Temperature: 25 ° C Solvent: Trifluoroethanol

Examples 1a to 17a and Comparative Examples 1a to 8a The hard surface liquid detergent compositions shown in Tables 1 and 2 were prepared using the following formulation components, and the following items were evaluated. The results are shown in Tables 1 and 2. Further, in the table, for convenience, the component (a') is represented by the component (a) and the mass ratio of (a)/(b) is shown. Further, the mass % of the blending components in Tables 1 and 2 are based on the values of the active ingredients. Further, the anionic surfactant of the component (c) represents a mass% based on the amount based on the sodium salt. The pH is adjusted with a small amount of sodium hydroxide and hydrochloric acid.

<Mixing component> (a) Component ・The copolymers A1 to A4 were used. (a') component (comparative component of component (a)) ・ Polymer A'1 was used. (b) Component: Cationic surfactant: alkyl dimethyl benzyl ammonium chloride: carbon number of alkyl group 8 (product name "Sanisol 08", manufactured by Kao (stock)) (c) Component, nonionic Surfactant: alkyl polyglycoside: alkyl (carbon number 12 to 16) polydextrose (average sugar condensation degree 1-2) (product name "AG124", manufactured by Kao (share)) ・ Amphoteric surfactant: Laurel Aminopropylcarboxybetaine (product name "Amphitol 20AB", manufactured by Kao (share)) ・ Anionic surfactant: sodium polyoxyalkylene ether sulfate, alkyl carbon number 12 to 16, epoxy B The average number of moles added to the alkane is 4.0 (product name "ES-4K", manufactured by Kao (share))

<Contact angle> 1 mL of a liquid detergent composition for a hard surface was applied to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., shape: 76 mm × 26 mm × 1 mm) and allowed to stand for 5 minutes, and then utilized 25 Rinse tap water (flow rate 50 mL/sec) at °C for 20 seconds. The static contact angle of the glass plate subjected to the above treatment to ion-exchanged water was measured in a measuring chamber where the temperature and humidity were adjusted to 25 ° C and 40% RH. In the measurement, a fully automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd. was used to drip 20 μl of ion-exchanged water droplets onto the treated surface, and after 10 seconds of dripping, 10 contact angles were measured at intervals of 1 second. The average value is recorded as information. Furthermore, the static contact angle of the glass plate before the treatment was 25°. The lower the contact angle, that is, the smaller the static contact angle with respect to the glass plate before the treatment, the more hydrophilized.

<Antifouling property (preventing soil adhesion)> The following one was used for the following evaluation: one side of the whole surface coating on a glass plate (manufactured by Songlang Glass Industry Co., Ltd., shape: 76 mm × 26 mm × 1 mm) 1 mL of the hard surface liquid detergent composition was allowed to stand for 5 minutes, and then obtained by rinsing with tap water (flow rate of 50 mL/sec) at 25 ° C for 20 seconds. Mix 450 ml of water with 50 ml of model oil solution (model oil: oleic acid, pigment: Sudan III (0.1 parts by mass relative to 100 parts by mass of oleic acid)) in a 500 ml beaker with a diameter of 10 cm to prepare the lower layer It is a liquid in which the upper layer is oil separated into two layers. The glass plate was immersed in the lower layer through the upper layer and immersed in the entire layer for 10 seconds, and then pulled out. Thereafter, after the immersed glass plate was dried, a photograph of the glass plate was taken, image processing was performed (using ImageJ), the residual area of the oil on the glass plate was measured, and the oil was calculated based on the treated area of the glass plate. Residual rate (first time). Thereafter, the operation was carried out by directly immersing for 10 seconds using a glass plate, and the residual ratio (second time) was calculated by the same method. The treated area of the glass was set to 100, and the residual ratio (%) was calculated from how much oil was coated on the surface (the degree of coating).

<Foaming ability> The hard surface was filled with a liquid detergent composition into a trigger spray container (Toilet Magiclean deodorizing washing spray, manufactured by Kao (Stock)), and the bubble expanding mode of the above container was applied to a 200 mL measuring cylinder ( Spray 10 times inside the inner diameter of 40 mm). The mass of the 200 mL graduated cylinder after the spray was measured using a four-digit balance, and the difference from the mass of the graduated cylinder before the spray was set as the bubble coating amount (g) (a). Further, the bubble volume (mL) (b) in the graduated cylinder after the spray was visually read. The bubble specific volume was calculated using the following formula. The results are shown in Tables 1 and 2. Bubble specific volume (mL/g) = (b) / (a) The larger the specific volume of the bubble, the more excellent the foaming ability.

<Removing power> Scraping Staphylococcus aureus (strain NBRC12732) on a nutrient agar medium (manufactured by Difco's Nutrient Agar reagent according to the efficacy specification) was repeated twice at 37 ° C / 24 hours to obtain a suspension Disperse in a 1/2 nutrient solution medium (manufactured by Difco, Inc., and prepare a Nuturient Broth reagent at a concentration of 1/2 of the efficacy specification), and prepare the bacterial concentration to 2.5 to 13 × 10 ⁸ using a 1/2 nutrient solution medium. Cfu/mL was mixed with an 3% by mass aqueous solution of bovine serum albumin in an equal volume to prepare a test bacterial solution. A stainless steel disc having a diameter of 20 mm, a thickness of 1 mm, and a surface grade of 2B was sterilized in a glass petri dish having an inner diameter of 75 mm, and the above test liquid was used using a micropipette (GILSON Corporation, trade name PIPETMAN). 10 μL was inoculated on the surface of the disc and spread. Placed under the condition of 25±1°C without covering the lid of the glass culture dish. After confirming that the bacterial solution is dried, quickly dilute the hard surface with the liquid detergent composition to 100 times with water adjusted to a hardness of 4°dH. Liquid adheres. Using a water having a hardness adjusted to 4°dH, the hard surface is diluted with a liquid detergent composition to a liquidity of 100 times. The adhesion is made using a micropipette (GILSON, trade name PIPETMAN) on a stainless steel disk surface of diameter 20 mm 3.14. The cm ² inoculation was carried out by diluting the hard surface with a liquid detergent composition diluted to 100 times the liquid 10 μL (corresponding to 0.32 g/100 cm ² ) with a hardness adjusted to 4°dH. After adhering for 5 minutes, while taking care of not adhering the combined stream, a certain amount of LP (lithium chloride-sodium propionate) aqueous dilution was prepared (according to the efficacy specification, manufactured by Rishui Pharmaceutical Co., Ltd.) In the case of the above, the sterilization performance of the composition was not activated, and the concentration of the bacteria in the LP water dilution solution was counted by the pour culture method. The physiological dilution should be used instead of the composition and the same operation (inoculation of 10 μL on the surface of the circular plate by inoculation with the above micropipette, and inoculation into the LP diluent after 5 minutes of inoculation) was used as a control operation to calculate the LP dilution. The logarithm of the number of bacteria in the liquid and the control operation was set as an indicator of the sterilization performance according to the following criteria. * Evaluation criteria for sterilizing power: The logarithmic difference of the number of bacteria is 2 or more B: the logarithmic difference of the number of bacteria is less than 2

<Preparation stability> The appearance of the liquid detergent composition for a hard surface immediately after preparation was visually observed at a liquid temperature of 20 ° C, and evaluated according to the following criteria. * Evaluation criteria for blending stability A: Dissolved evenly. B: Slightly cloudy. C: Obvious turbidity.

[Table 1]

[Table 2]

Examples 1b to 9b and Comparative Examples 1b to 4b The hard surface liquid detergent compositions shown in Table 3 were prepared using the following formulation components, and the following items were evaluated. The results are shown in Table 3. Further, the mass % of the formulated components in Table 3 is based on the value of the active ingredient. Further, in the table, for convenience, the component (a') is represented by the component (a) and the mass ratio of (a)/(b) is shown. Further, the mass ratio of (b)/(d) represents a value calculated based on the mass % of the acid of the component (d). Further, the pH is adjusted with a small amount of sodium hydroxide or hydrochloric acid.

<Mixing component> (a) Component ・ The copolymer A1 of the above Production Example 1 and the copolymer A4 of the above Production Example 4 were used. (a') component (comparative component of component (a)) ・ The polymer A'1 of the above Production Example 5 was used. (b) Component: Cationic surfactant: alkyl dimethyl benzyl ammonium chloride: carbon number of alkyl 8 (product name "Sanisol 08", manufactured by Kao (share)) (d) component EDTA: B Diaminetetraacetic acid, tetrasodium salt (the number in the table is % by mass of the sodium salt, and the number in parentheses is the mass % of the acid). Other components ・Nonionic surfactant: alkyl polyglycoside: alkyl group (Colour number 12 to 16) Polydextrose (average sugar condensation degree 1 to 2) (product name "AG124", manufactured by Kao (share)) ・ Amphoteric surfactant: Laurel propyl carboxycarboxybetaine (product name "Amphitol" 20AB", manufactured by Kao (share)

<Contact Angle> The static contact angle was measured in the same manner as in Example 1a and the like.

<Antifouling property (preventing soil adhesion)> The following one was used for the following evaluation: one side of the whole surface coating on a glass plate (manufactured by Songlang Glass Industry Co., Ltd., shape: 76 mm × 26 mm × 1 mm) 1 mL of the hard surface liquid detergent composition was allowed to stand for 5 minutes, and then obtained by rinsing with tap water (flow rate of 50 mL/sec) at 25 ° C for 20 seconds. Mix 450 ml of water with 50 ml of model oil solution (model oil: oleic acid, pigment: Sudan III (0.1 parts by mass relative to 100 parts by mass of oleic acid)) in a 500 ml beaker with a diameter of 10 cm to prepare the lower layer It is a liquid in which the upper layer is oil separated into two layers. The glass plate was immersed in the lower layer through the upper layer and immersed in the entire layer for 10 seconds, and then pulled out. Thereafter, after the immersed glass plate was dried, a photograph of the glass plate was taken, image processing was performed (using Image J), and the residual area of the oil on the glass plate was measured, and the oil was calculated based on the treated area of the glass plate. Residual rate. The treated area of the glass was set to 100, and the residual ratio (%) was calculated from how much oil was coated on the surface (the degree of coating). The antifouling property was evaluated based on the residual ratio based on the following criteria. *Evaluation criteria for antifouling properties A: Residual rate is less than 10% B: Residual rate is 10% or more

<Detergency (Removal of Scale)> 2 ml of a 0.5% aqueous solution of calcium dihydrogen phosphate was uniformly applied to a black ceramic plate (10 cm × 10 cm tile) as a model of dirt and allowed to be at 120 ° C. Dry for 30 minutes. This operation was repeated 10 times to prepare a model contamination plate, and the cleaning power test was performed using the same. The composition was dropped (0.3 ml) to the above-mentioned model-contained plate fixed horizontally, left for 1 minute, and then washed with a cotton swab 10 times to wash. In the same conditions as the brightness and the like, the image is obtained from the pottery board that has not been coated with dirt, the pottery board (model contamination board) before washing, and the washed pottery board. The image measures the gray scale of each pottery plate. The pottery board before the dirt washing was set to a washing rate of 0%, and the uncoated soil pottery board was set to a washing rate of 100%, and the washing rate of the pottery board was calculated in comparison with the state of the washed pottery board. . Furthermore, Image J1.47v of the image processing software was used to measure the gradation.

<Removing power> The sterilizing power was evaluated in the same manner as in Example 1a and the like.

<Mixing stability> The formulation stability was evaluated in the same manner as in Example 1a and the like.

<Foaming ability> The hard surface was filled with a liquid detergent composition into a trigger spray container (Toilet Magiclean deodorizing washing spray, manufactured by Kao (Stock)), and the bubble expanding mode of the above container was applied to a 200 mL measuring cylinder ( Spray 10 times inside the inner diameter of 40 mm). The mass of the 200 mL graduated cylinder after the spray was measured using a four-digit balance, and the difference from the mass of the graduated cylinder before the spray was set as the bubble coating amount (g) (a). Further, the bubble volume (mL) (b) in the graduated cylinder after the spray was visually read. The bubble specific volume was calculated using the following formula. The results are shown in Table 3. Bubble specific volume (mL/g) = (b) / (a) The larger the specific volume of the bubble, the more excellent the foaming ability. The foaming performance was evaluated in accordance with the following criteria based on the specific volume of the foam. *Evaluation criteria for foaming performance A: The specific volume of the foam is 10 mL/g or more B: The specific volume of the foam is 5 mL/g or more and less than 10 mL/g C: The specific volume of the foam is less than 5 mL/g

[table 3]

Claims (8)

A liquid detergent composition for a hard surface, comprising: (a) a structural unit (a1) represented by the following formula (1); and a structural unit (a2) represented by the following formula (2) and having a structure The molar ratio of the unit (a1) to the structural unit (a2), that is, the structural unit (a1)/structural unit (a2) is a copolymer of 30/70 or more and 99.9/0.1 or less [hereinafter referred to as (a) component], ( b) a cationic surfactant (hereinafter referred to as component (b)), and (c) one or more surfactants selected from the group consisting of an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant [ Called as (c) component]; [Chemical 1] Wherein R ¹ to R ^{3 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; and R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, or -Y ¹ -OPO ₃ ^- - Y ² -, Y ¹ and Y ^{2 are the} same or different and are an alkylene group having 1 or more and 4 or less carbon atoms, and R ⁵ and R ^{6 are the} same or different, and are a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ¹ is O. Or NR ⁷ , R ⁷ is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ² represents a hydrogen atom, a hydrocarbon group having 1 or more and 4 or less carbon atoms, R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- ; When R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, X ² is R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- , and R ¹⁷ is an alkylene group having 1 or more and 4 or less carbon atoms, and is R ^{4 .} When -Y ¹ -OPO ₃ ^- -Y ² -, X ² is a hydrogen atom or a hydrocarbon group having a carbon number of 1 or more and 4 or less] [Chemical 2] Wherein R ⁸ to R ^{10 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; X ³ is O; R ¹¹ is an alkylene group having 1 or more and 4 or less carbon atoms, and X ⁴ is N. ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ , and R ¹² to R ^{16 are the} same or different and each represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ⁵ represents an anion]. The liquid detergent composition for a hard surface according to claim 1, wherein the mass ratio of (b)/(c) is 0.05 or more and 30 or less. A liquid detergent composition for a hard surface, comprising: (a) a structural unit (a1) represented by the following formula (1); and a structural unit (a2) represented by the following formula (2) and having a structure The molar ratio of the unit (a1) to the structural unit (a2), that is, the structural unit (a1)/structural unit (a2) is a copolymer of 30/70 or more and 99.9/0.1 or less [hereinafter referred to as (a) component], ( b) a cationic surfactant [hereinafter referred to as component (b)], and (d) a chelating agent [hereinafter referred to as component (d)]; [Chemical 3] Wherein R ¹ to R ^{3 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; and R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, or -Y ¹ -OPO ₃ ^- - Y ² -, Y ¹ and Y ^{2 are the} same or different and are an alkylene group having 1 or more and 4 or less carbon atoms, and R ⁵ and R ^{6 are the} same or different, and are a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ¹ is O. Or NR ⁷ , R ⁷ is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ² represents a hydrogen atom, a hydrocarbon group having 1 or more and 4 or less carbon atoms, R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- ; When R ⁴ is an alkylene group having 1 or more and 4 or less carbon atoms, X ² is R ¹⁷ SO ₃ ^- or R ¹⁷ COO ^- , and R ¹⁷ is an alkylene group having 1 or more and 4 or less carbon atoms, and is R ^{4 .} When -Y ¹ -OPO ₃ ^- -Y ² -, X ² is a hydrogen atom or a hydrocarbon group having a carbon number of 1 or more and 4 or less] [Chemical 4] Wherein R ⁸ to R ^{10 are the} same or different and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; X ³ is O; R ¹¹ is an alkylene group having 1 or more and 4 or less carbon atoms, and X ⁴ is N. ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ , and R ¹² to R ^{16 are the} same or different and each represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and X ⁵ represents an anion]. The liquid surface cleaner composition for hard surfaces according to claim 3, wherein the mass ratio of (b) / (d) is 0.01 or more and 10 or less. The liquid detergent composition for a hard surface according to any one of claims 1 to 4, wherein the content of the component (a) is 0.01% by mass or more and 3% by mass or less. The liquid detergent composition for a hard surface according to any one of claims 1 to 5, wherein the mass ratio of (a)/(b) is 0.01 or more and 5 or less. The hard surface liquid detergent composition according to any one of claims 1 to 6, wherein the hard surface is a hydrophilic hard surface. A method of preventing fouling of a hard surface by treating a hard surface with a liquid detergent composition for a hard surface according to any one of claims 1 to 7.